WO2020194928A1 - Coating composition - Google Patents

Abstract

A coating composition which contains (A) a binder component, (B) a first viscosity regulating agent and (C) a second viscosity regulating agent, and which is configured such that: the first viscosity regulating agent (B) is a nonaqueous dispersion resin (b); the second viscosity regulating agent (C) contains a reaction product of (c1) a polyisocyanate compound, (c2) a primary monoamine that has a number average molecular weight of 300 or less and (c3) a polyether amine that has two or more amino groups, while having a number average molecular weight of 1,000 or more but less than 6,000; and the blending ratio of the polyether amine (c3) that has two or more amino groups, while having a number average molecular weight of 1,000 or more but less than 6,000 is within the range of 10-30% by mass based on the total amount of the components (c1)-(c3).

Description

Paint composition

The present invention relates to a coating composition.

Conventionally, for the purpose of imparting excellent appearance, performance, etc. to an object to be coated, a coating composition is applied onto the object to be coated, and the formed wet coating film is cured to form a coating film. Is being done.

Among these, when the object to be coated has a vertical surface, there is a problem that the wet coating film coated on the vertical surface drips and the appearance of the formed coating film deteriorates. For this reason, studies have been conducted on coating compositions containing a viscosity modifier (rheology control agent) having an ability to suppress sagging.

For example, Patent Document 1 describes a coating composition containing a binder component and a viscosity adjusting agent, and the viscosity adjusting agent includes a polyisocyanate compound, a primary monoamine having a number average molecular weight of 300 or less, and a number average molecular weight of 300. Viscosity modifiers containing reaction products of polyether amines greater than 6000 are used.

International Publication WO2018 / 012552

The coating film formed by the coating composition described in Patent Document 1 can form a coating film having excellent transparency, water resistance and finished appearance, but has sagging resistance and the finished appearance of the formed coating film. Further improvement in water whitening resistance is desired.

The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a coating composition having excellent sagging resistance at the time of coating and excellent finished appearance and water whitening resistance of the formed coating film. To do.

As a result of diligent studies to achieve the above object, the present inventors have made a coating composition containing (A) a binder component, (B) a first viscosity modifier, and (C) a second viscosity modifier. The first viscosity modifier (B) is a non-aqueous dispersion resin (b), and the second viscosity modifier (C) is a (c1) polyisocyanate compound, (c2) number average. It contains a reaction product of a primary monoamine having a molecular weight of 300 or less and a polyetheramine having two or more (c3) amino groups and having a number average molecular weight of 1000 or more and less than 6000, and has two amino groups. The blending ratio of the polyether amine (c3) having the above and having a number average molecular weight of 1000 or more and less than 6000 is in the range of 10 to 30% by mass based on the total amount of the components (c1) to (c3). It was found that the above-mentioned object can be achieved according to the coating composition in the above.

That is, the present invention includes the following aspects.

In one embodiment, a coating composition containing (A) a binder component, (B) a first viscosity modifier, and (C) a second viscosity modifier, wherein the first viscosity modifier (B) Is a non-aqueous dispersion resin (b), and the second viscosity modifier (C) is a (c1) polyisocyanate compound, (c2) a primary monoamine having a number average molecular weight of 300 or less, and (c3) amino. Contains reaction products of polyetheramines having two or more groups and having a number average molecular weight of 1000 or more and less than 6000.
The blending ratio of the polyether amine (c3) having two or more amino groups and having a number average molecular weight of 1000 or more and less than 6000 is 10 based on the total amount of the components (c1) to (c3). A coating composition in the range of ~ 30% by weight is provided.

In another embodiment, the polyether amine (c3) having two or more amino groups and having a number average molecular weight of 1000 or more and less than 6000 has three or more amino groups.

In another embodiment, the blending ratio of the polyether amine (c3) having two or more amino groups and having a number average molecular weight of 1000 or more and less than 6000 is the total of the components (c1) to (c3). It is in the range of 15 to 30% by mass based on the amount.

In another embodiment, the binder component (A) contains a hydroxyl group-containing resin (A1) and a cross-linking agent (A2).

According to the coating composition of the present invention, it is possible to form a coating film having excellent sagging resistance at the time of coating and excellent finished appearance and water whitening resistance.

Hereinafter, the coating composition of the present invention will be described in more detail.

Binder component (A)
The binder component (A) itself has a film-forming property, and may be either a non-crosslinked type or a crosslinked type, and a crosslinked type is preferable. As the binder component (A), a film-forming resin known per se can be used, which has been conventionally used as a binder component for paints.

Examples of the type of the film-forming resin include acrylic resin, polyester resin, alkyd resin, polyurethane resin and the like. The film-forming resin preferably has a crosslinkable functional group such as a hydroxyl group, a carboxyl group, or an epoxy group.

Further, as the binder component (A), a cross-linking agent can be used in addition to the film-forming resin. When the cross-linking agent is used as a part of the binder component (A), the film-forming resin usually has a cross-linking functional group such as a hydroxyl group, a carboxyl group, or an epoxy group, and reacts with the cross-linking agent. Therefore, a resin (base resin) capable of forming a crosslinked film can be used. The coating composition of the present invention is preferably a crosslinked coating material containing the above-mentioned substrate resin and a crosslinking agent from the viewpoint of water resistance of the formed coating film and the like.

Among them, in the coating composition of the present invention, at least a part of the base resin contains a hydroxyl group-containing resin (A1), and at least a part of the cross-linking agent has reactivity with the hydroxyl group-containing resin. It is preferable to contain a cross-linking agent (A2).

Hydroxy group-containing resin (A1)
The hydroxyl group-containing resin (A1) is a resin having at least one hydroxyl group in one molecule. As the hydroxyl group-containing resin (A1), known resins can be widely used. For example, acrylic resin having a hydroxyl group, polyester resin having a hydroxyl group, acrylic modified polyester resin having a hydroxyl group, polyether resin having a hydroxyl group, and polycarbonate having a hydroxyl group. Examples thereof include resins, polyurethane resins having a hydroxyl group, epoxy resins having a hydroxyl group, and alkyd resins having a hydroxyl group. These can be used alone or in combination of two or more. Among them, the hydroxyl group-containing resin (A1) is preferably a hydroxyl group-containing acrylic resin (A1-1) from the viewpoint of water resistance of the formed coating film and the like.

Hydroxy group-containing acrylic resin (A1-1)
The hydroxyl group-containing acrylic resin (A1-1) is obtained by, for example, copolymerizing a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer (a polymerizable unsaturated monomer other than the hydroxyl group-containing polymerizable unsaturated monomer). Obtainable.

The hydroxyl group-containing polymerizable unsaturated monomer is a compound having one or more hydroxyl groups and one or more polymerizable unsaturated bonds in one molecule. Examples of the hydroxyl group-containing polymerizable unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. A monoesterified product of (meth) acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms; an ε-caprolactone modified product of the monoesterified product of the (meth) acrylic acid and a divalent alcohol having 2 to 8 carbon atoms; Additives of (meth) acrylic acid and epoxy group-containing compounds (eg, "Cadura E10P" (trade name), Momentive Specialty Chemicals, neodecanoic acid glycidyl ester); N-hydroxymethyl (meth) acrylamide; allyl alcohol, and further. , (Meta) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end can be mentioned.

As the other polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, for example, the monomers shown in (1) to (6) below can be used. These polymerizable unsaturated monomers can be used alone or in combination of two or more.

(1) Acid Group-Containing Polymerizable Unsaturated Monomer An acid group-containing polymerizable unsaturated monomer is a compound having one or more acid groups and one or more polymerizable unsaturated bonds in one molecule. Examples of the monomer include carboxyl group-containing monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and maleic anhydride; sulfonic acid group-containing monomers such as vinyl sulfonic acid and 2-sulfoethyl (meth) acrylate. Acids such as 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3-chloropropyl acid phosphate, 2-methacryloyloxyethyl phenyl phosphate Examples thereof include phosphoric acid ester-based monomers. These can be used alone or in combination of two or more. When an acid group-containing polymerizable unsaturated monomer is used, the acid value of the hydroxyl group-containing acrylic resin (A1-1) is preferably 0.5 to 15 mgKOH / g, more preferably 1 to 10 mgKOH / g. ..

(2) Esteride of acrylic acid or methacrylic acid and a monovalent alcohol having 1 to 20 carbon atoms Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth). ) Acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, isostearyl acrylate (Osaka Organic) Chemical Industry Co., Ltd., trade name), lauryl (meth) acrylate, tridecyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and the like can be mentioned.

(3) Aromatic Vinyl Monomer Specific examples thereof include styrene, α-methylstyrene and vinyltoluene.

By using an aromatic vinyl monomer as a constituent component, the glass transition temperature of the obtained resin rises, and a hydrophobic coating film with a high refractive index can be obtained. Therefore, the finished appearance by improving the gloss of the coating film. The improvement effect of can be obtained.

When an aromatic vinyl monomer is used as a constituent component, the blending ratio thereof is preferably in the range of 3 to 50% by mass, more preferably 5 to 40% by mass, based on the total amount of the monomer components.

(4) Glycidyl group-containing polymerizable unsaturated monomer The glycidyl group-containing polymerizable unsaturated monomer is a compound having one or more glycidyl groups and one or more polymerizable unsaturated bonds in one molecule, and specifically, glycidyl. Examples thereof include acrylate and glycidyl methacrylate.

(5) Polymerizable unsaturated bond-containing nitrogen atom-containing compound For example, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N- [3- (dimethylamino) propyl] (meth) acrylamide, N-butoxymethyl. Examples thereof include (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, vinylpyridine, vinylimidazole, acrylonitrile, and methacrylonitrile.

(6) Other Vinyl Compounds For example, vinyl acetate, vinyl propionate, vinyl chloride, vinyl versatic acid ester and the like can be mentioned. Examples of the versatic acid vinyl ester include commercially available products such as "Beova 9" and "Beova 10" (above, trade name, manufactured by Japan Epoxy Resin Co., Ltd.).

As the other polymerizable unsaturated monomer, one kind or two or more kinds of the monomers shown in (1) to (6) above can be used.

In the present invention, the polymerizable unsaturated monomer means a monomer having one or more (for example, 1 to 4) polymerizable unsaturated groups. The polymerizable unsaturated group means an unsaturated group capable of radical polymerization. Examples of such polymerizable unsaturated group include a vinyl group, a (meth) acryloyl group, a (meth) acrylamide group, a vinyl ether group, an allyl group, a propenyl group, an isopropenyl group, a maleimide group and the like.

Further, in the present specification, "(meth) acrylate" means acrylate or methacrylate. "(Meta) acrylic acid" means acrylic acid or methacrylic acid. In addition, "(meth) acryloyl" means acryloyl or methacryloyl. In addition, "(meth) acrylamide" means acrylamide or methacrylamide.

The hydroxyl value of the hydroxyl group-containing acrylic resin (A1-1) is preferably 70 to 200 mgKOH / g, more preferably 80 to 185 mgKOH / g, and particularly preferably 100 to 170 mgKOH / g from the viewpoint of curability and water resistance. Is within the range of.

The weight average molecular weight of the hydroxyl group-containing acrylic resin (A1-1) is preferably 2000 to 50,000, more preferably 3000 to 30000, and particularly preferably 4000, from the viewpoint of the finished appearance and curability of the coating film. It is in the range of ~ 10,000.

In the present specification, the average molecular weight is a value calculated from a chromatogram measured by a gel permeation chromatograph based on the molecular weight of standard polystyrene. As the gel permeation chromatograph, "HLC8120GPC" (manufactured by Tosoh Corporation) was used. As columns, four columns of "TSKgel G-4000HXL", "TSKgel G-3000HXL", "TSKgel G-2500HXL", and "TSKgel G-2000HXL" (all manufactured by Tosoh Corporation, trade name) are used. The procedure was carried out under the conditions of mobile phase; tetrahydrofuran, measurement temperature; 40 ° C., flow rate; 1 cc / min, detector; RI.

The glass transition temperature of the hydroxyl group-containing acrylic resin (A1-1) is preferably −50 to 60 ° C., more preferably 10 to 50 ° C., and particularly preferably 20 to 20 ° C. from the viewpoint of the hardness of the coating film and the finished appearance. It is within the range of 45 ° C.

In the present specification, the glass transition temperature (° C.) of the acrylic resin was calculated by the following formula.

1 / Tg (K) = (W1 / T1) + (W2 / T2) + ... (1)
Tg (° C.) = Tg (K) -273 (2)
In each formula, W1, W2, ... Represent the mass fraction of each of the monomers used in the copolymerization, and T1, T2, ... Represent the Tg (K) of the homopolymer of each monomer.
In addition, T1, T2, ... Are the values according to Polymer Hand Book (Edited by Second Edition, J. Brandup, E. H. Immunogut) III-139 to 179. The glass transition temperature (° C.) when the Tg of the homopolymer of the monomer is not clear is a static glass transition temperature, and for example, a differential scanning calorimeter "DSC-220U" (manufactured by Seiko Instruments) is used. The sample is placed in a measuring cup, vacuum sucked to completely remove the solvent, and then the calorific value change is measured in the range of -20 ° C to + 200 ° C at a heating rate of 3 ° C / min, and the first baseline on the low temperature side. The change point was the static glass transition temperature.

The acid value of the hydroxyl group-containing acrylic resin (A1-1) is preferably in the range of 0.5 to 15 mgKOH / g, more preferably 1 to 10 mgKOH / g from the viewpoint of the pot life of the coating composition and the finished appearance. Is inside.

The copolymerization method for copolymerizing the above-mentioned monomer mixture to obtain a hydroxyl group-containing acrylic resin (A1-1) is not particularly limited, and a copolymerization method known per se can be used. A solution polymerization method in which polymerization is carried out in an organic solvent in the presence of a polymerization initiator can be preferably used.

Examples of the organic solvent used in the above solution polymerization method include aromatic solvents such as toluene, xylene, and swazole 1000 (manufactured by Cosmo Petroleum Co., Ltd., trade name, high boiling petroleum solvent); ethyl acetate, butyl acetate, propyl Ester solvents such as propionate, butyl propionate, 1-methoxy-2-propyl acetate, 2-ethoxyethyl propionate, 3-methoxybutyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate; methyl ethyl ketone , Methylisobutylketone, methylamylketone and other ketone solvents, isopropanol, n-butanol, isobutanol, 2-ethylhexanol and other alcoholic solvents and the like.

These organic solvents can be used alone or in combination of two or more, but it is preferable to use an ester solvent or a ketone solvent from the viewpoint of the solubility of the acrylic resin. Further, it is also possible to use an aromatic solvent in a suitable combination.

Examples of the polymerization initiator that can be used in the copolymerization of the hydroxyl group-containing acrylic resin (A1-1) include 2,2'-azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, and di-t. -Known radical polymerization initiators such as-amyl peroxide, t-butyl peroctate, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) Can be mentioned.

The hydroxyl group-containing acrylic resin (A1-1) can be used alone or in combination of two or more.

Secondary hydroxyl group-containing acrylic resin (A1-1a)
As one of the embodiments of the hydroxyl group-containing acrylic resin (A1-1), a secondary hydroxyl group-containing acrylic resin (A1-1a) can be preferably used from the viewpoint of the finished appearance of the formed coating film.

The secondary hydroxyl group-containing acrylic resin (A1-1a) is, for example, a secondary hydroxyl group-containing polymerizable monomer as one of the hydroxyl group-containing polymerizable unsaturated monomers in the method for producing the hydroxyl group-containing acrylic resin (A1-1). It can be produced by using an unsaturated monomer.

Examples of the secondary hydroxyl group-containing polymerizable unsaturated monomer include carbon of the alkyl group in the ester portion of 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate and the like. A polymerizable unsaturated monomer having a secondary hydroxyl group having a number of 2 to 8, preferably 3 to 6, and more preferably 3 or 4; (meth) acrylic acid and an epoxy group-containing compound (for example, "Cadura E10P" (trade name) ), Additives with Monomer Specialty Chemicals, neodecanoic acid glycidyl ester) and the like. These can be used alone or in combination of two or more. Among them, 2-hydroxypropyl (meth) acrylate can be preferably used from the viewpoint of the finished appearance of the formed coating film.

When the secondary hydroxyl group-containing polymerizable unsaturated monomer is used in the production of the secondary hydroxyl group-containing acrylic resin (A1-1a), the amount of the secondary hydroxyl group-containing polymerizable unsaturated monomer used is the coating formed. From the viewpoint of the finished appearance of the film, the amount is preferably 15 to 45% by mass, more preferably 20 to 40% by mass, based on the total amount of the copolymerization monomer components constituting the secondary hydroxyl group-containing acrylic resin (A1-1a). It is within the range.

Further, in the secondary hydroxyl group-containing acrylic resin (A1-1a), the content ratio of the secondary hydroxyl group-containing polymerizable unsaturated monomer in the total amount of the hydroxyl group-containing polymerizable unsaturated monomer is the water resistance of the formed coating film. From the viewpoint of finished appearance and the like, it is preferably in the range of 50 to 100% by mass, more preferably 55 to 100% by mass, and further preferably 60 to 100% by mass.

Acrylic resin having a hydroxyl group and an alkoxysilyl group (A1-1b)
As one of the other aspects of the hydroxyl group-containing acrylic resin (A1-1), an acrylic resin (A1-1b) having a hydroxyl group and an alkoxysilyl group is preferably used from the viewpoint of scratch resistance of the formed coating film. Can be used.

Acrylic resin (A1-1b) having a hydroxyl group and an alkoxysilyl group is a resin having at least one hydroxyl group and one alkoxysilyl group in one molecule.

By using an acrylic resin (A1-1b) having a hydroxyl group and an alkoxysilyl group, the curability of the coating film is improved by forming a cross-linking reaction between the alkoxyryl groups and the reaction between the alkoxysilyl group and the hydroxyl group. Can be made to.

The alkoxy portion of the alkoxysilyl group contained in the acrylic resin (A1-1b) having a hydroxyl group and an alkoxysilyl group is an alkoxy having about 1 to 6 carbon atoms such as methoxy, ethoxy, and propoxy, preferably about 1 to 3 carbon atoms. The part is illustrated. As the alkoxy moiety, methoxy and ethoxy are more preferable, and methoxy is particularly preferable, from the viewpoint of scratch resistance and the like of the formed coating film.

The alkoxysilyl group includes a trialkoxysilyl group, a dialkoxysilyl group and a monoalkoxysilyl group. As the alkoxysilyl group, a trialkoxysilyl group is preferable from the viewpoint of scratch resistance and the like of the formed coating film.

When the alkoxysilyl group is a dialkoxysilyl group or a monoalkoxysilyl group, an alkyl having about 1 to 6 carbon atoms, preferably about 1 to 3 carbon atoms (for example, methyl) is used as a group other than alkoxy bonded to a silicon atom. , Ethyl, propyl).

The acrylic resin (A1-1b) having a hydroxyl group and an alkoxysilyl group is, for example, an alkoxysilyl group-containing polymerization as one of the polymerizable unsaturated monomers in the method for producing the hydroxyl group-containing acrylic resin (A1-1). It can be obtained by using a sex unsaturated monomer and other polymerizable unsaturated monomer.

The alkoxysilyl group-containing polymerizable unsaturated monomer is a compound having one or more alkoxysilyl groups and one or more polymerizable unsaturated bonds in one molecule. Examples of the alkoxysilyl group-containing polymerizable unsaturated monomer include vinyltrimethoxysilane, vinyltriethoxysilane, acryloxyethyltrimethoxysilane, metharoxyethyltrimethoxysilane, acryloxipropyltrimethoxysilane, and metharoxypropyltri. Examples thereof include methoxysilane, acryloxipropyltriethoxysilane, methacryoxypropyltriethoxysilane, vinyltris (β-methoxyethoxy) silane and the like.

The alkoxysilyl group-containing polymerizable unsaturated monomer includes vinyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane from the viewpoint of scratch resistance of the formed coating film. Is preferable, and γ-methacryloxypropyltrimethoxysilane is more preferable.

A commercially available product can be used as the alkoxysilyl group-containing polymerizable unsaturated monomer. For example, KBM-1003, KBE-1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-5803 (all manufactured by Shin-Etsu Chemical Co., Ltd.), Y-9936, A. -174 (manufactured by Momentive Performance Materials Japan GK), OFS-6030, Z-6033 (manufactured by Toray Dow Corning Co., Ltd.) can be mentioned.

The above-mentioned alkoxysilyl group-containing polymerizable unsaturated monomer can be used alone or in combination of two or more.

That is, the acrylic resin (A1-1b) having a hydroxyl group and an alkoxysilyl group is, for example, the hydroxyl group-containing polymerizable unsaturated monomer, the alkoxysilyl group-containing polymerizable unsaturated monomer, and other polymerizable unsaturated monomer (hydroxyl-containing). It can be obtained by copolymerizing a polymerizable unsaturated monomer other than the polymerizable unsaturated monomer and the alkoxysilyl group-containing polymerizable unsaturated monomer). As the other copolymerizable unsaturated monomer, for example, other polymerizable unsaturated monomers (1) to (6) used for obtaining the hydroxyl group-containing acrylic resin (A1-1) can be used. .. The polymerizable unsaturated monomer can be used alone or in combination of two or more.

In the production of the acrylic resin (A1-1b) having a hydroxyl group and an alkoxysilyl group, the amount of the hydroxyl group-containing polymerizable unsaturated monomer used depends on the scratch resistance, water resistance, curability, finished appearance, etc. of the formed coating film. From the viewpoint of the above, preferably 5 to 60% by mass, more preferably 15 to 50% by mass, still more preferably, with respect to the total amount of the copolymerization monomer components constituting the acrylic resin (A1-1b) having a hydroxyl group and an alkoxysilyl group. Is in the range of 25 to 45% by mass.

The hydroxyl value of the acrylic resin (A1-1b) having a hydroxyl group and an alkoxysilyl group is preferably 70 to 200 mgKOH / g from the viewpoint of scratch resistance, water resistance, curability, finished appearance, etc. of the formed coating film. , More preferably in the range of 80 to 190 mgKOH / g, and even more preferably in the range of 100 to 180 mgKOH / g.

Acrylic resin having a secondary hydroxyl group and an alkoxysilyl group (A1-1c)
As one of the other aspects of the hydroxyl group-containing acrylic resin (A1-1), an acrylic resin (A1-1c) having a secondary hydroxyl group and an alkoxysilyl group is used from the viewpoint of the finished appearance of the formed coating film. can do.

The acrylic resin (A1-1c) having a secondary hydroxyl group and an alkoxysilyl group is a combination of the secondary hydroxyl group-containing acrylic resin (A1-1a) and the acrylic resin having a hydroxyl group and an alkoxysilyl group (A1-1b), respectively. Included.

The acrylic resin (A1-1c) having a secondary hydroxyl group and an alkoxysilyl group is, for example, the hydroxyl group-containing polymerizable unsaturated monomer in the method for producing an acrylic resin (A1-1b) having a hydroxyl group and an alkoxysilyl group. As one kind, it is produced by using a secondary hydroxyl group-containing polymerizable unsaturated monomer (for example, a secondary hydroxyl group-containing polymerizable unsaturated monomer that can be used for producing the above-mentioned secondary hydroxyl group-containing acrylic resin (A1-1a)). be able to.

When the secondary hydroxyl group-containing polymerizable unsaturated monomer is used in the production of the acrylic resin (A1-1c) having the secondary hydroxyl group and the alkoxysilyl group, the amount of the secondary hydroxyl group-containing polymerizable unsaturated monomer used is From the viewpoint of the finished appearance of the formed coating film, preferably 15 to 45% by mass with respect to the total amount of the copolymerization monomer components constituting the acrylic resin (A1-1c) having a secondary hydroxyl group and an alkoxysilyl group. , More preferably in the range of 20-40% by mass.

Further, in the production of the acrylic resin (A1-1c) having the secondary hydroxyl group and the alkoxysilyl group, the content ratio of the secondary hydroxyl group-containing polymerizable unsaturated monomer in the total amount of the hydroxyl group-containing polymerizable unsaturated monomer is formed. From the viewpoint of water resistance, finished appearance, etc. of the coating film to be coated, it is preferably in the range of 50 to 100% by mass, more preferably 55 to 100% by mass, and further preferably 60 to 100% by mass.

Further, in the coating composition of the present invention, as the film-forming resin other than the above that can be used as the binder component (A), for example, an acrylic resin containing no hydroxyl group, a hydroxyl group-containing resin, or a hydroxyl group-containing resin is contained. Examples thereof include polyester resins that do not contain hydroxyl groups, polyether resins that contain or do not contain hydroxyl groups, and polyurethane resins that contain or do not contain hydroxyl groups. Among them, preferred examples of the film-forming resin include a hydroxyl group-containing polyester resin and a hydroxyl group-containing polyurethane resin.

The hydroxyl group-containing polyester resin can be produced by a conventional method, for example, by an esterification reaction of a polybasic acid and a polyvalent alcohol. The polybasic acid is a compound having two or more carboxyl groups in one molecule, and is, for example, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic acid, hexa. Examples thereof include hydrophthalic acid, maleic acid, fumaric acid, itaconic acid, trimellitic acid, pyromellitic acid and anhydrides thereof. The polyhydric alcohol is a compound having two or more hydroxyl groups in one molecule, and is, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, or 1,5-pentane. Diol, 1,6-hexanediol, 2,2-diethyl-1,3-propanediol, neopentyl glycol, 1,9-nonanediol, 1,4-cyclohexanediol, hydroxypivalate neopentyl glycol ester, 2- Diols such as butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethylpentanediol, bisphenol hydride A, and trimethylpropane, trimethylol. Trivalent or higher polyol components such as ethane, glycerin, and pentaerythritol, as well as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, and 2,2-dimethylol. Examples thereof include hydroxycarboxylic acids such as hexanoic acid and 2,2-dimethylol octanoic acid.

In addition, α-olefin epoxides such as propylene oxide and butylene oxide, and monoepoxy compounds such as "Cadura E10P" (manufactured by Momentive Specialty Chemicals, trade name, glycidyl ester of synthetic highly branched saturated fatty acid) are reacted with an acid. These compounds may be introduced into the polyester resin.

When introducing a carboxyl group into a polyester resin, for example, it can be introduced by adding anhydrous acid to a hydroxyl group-containing polyester and half-esterifying it.

The hydroxyl value of the hydroxyl group-containing polyester resin is preferably in the range of 80 to 250 mgKOH / g, more preferably 100 to 200 mgKOH / g. The weight average molecular weight of the hydroxyl group-containing polyester resin is preferably in the range of 500 to 3500, more preferably 500 to 2500.

Examples of the hydroxyl group-containing polyurethane resin include a hydroxyl group-containing polyurethane resin obtained by reacting a polyol with a polyisocyanate.

Examples of the polyol include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol and hexamethylene glycol, and trihydric alcohols such as trimethylolpropane, glycerin and pentaerythritol. Can be done. Examples of high molecular weight substances include polyether polyols, polyester polyols, acrylic polyols, epoxy polyols and the like. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like. The polyester polyol includes the above-mentioned dihydric alcohol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and other alcohols, and dibasic acids such as adipic acid, azelaic acid and sebatic acid. Examples thereof include polycondensates of the above, lactone-based ring-opening polymer polyols such as polycaprolactone, and polycarbonate diols. Further, for example, carboxyl group-containing polyols such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid can also be used.

Examples of the polyisocyanate to be reacted with the above polyol include aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimersate diisocyanate, and lysine diisocyanate; and addition of these polyisocyanates to a burette type. Isocyanurate ring adduct; isophorone diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), methylcyclohexane-2,4- (or -2,6-) diisocyanate, 1,3- (or 1,4-) Alicyclic diisocyanates such as di (isocyanatomethyl) cyclohexane, 1,4-cyclohexanediisocyanate, 1,3-cyclopentanediisocyanate, 1,2-cyclohexanediisocyanate; and burette-type adducts of these polyisocyanates, isocyanate Nurate ring adduct; xylylene diisocyanate, metaxylylene diisocyanate, tetramethylxylylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalenedi isocyanate, 1,4-naphthalenedi isocyanate, 4,4- Truizin diisocyanate, 4,4'-diphenyl ether diisocyanate, (m- or p-) phenylenediisocyanate, 4,4'-biphenylenediisocyanate, 3,3'-dimethyl-4,4'-biphenylenediocyanate, bis (4-isocyanato) Aromatic diisocyanate compounds such as phenyl) sulfone, isopropyridenebis (4-phenylisocyanate); and burette-type adducts, isocyanurate ring adducts of these polyisocyanates; triphenylmethane-4,4', 4'' -One molecule of triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 4,4'-dimethyldiphenylmethane-2,2', 5,5'-tetraisocyanate, etc. Polyisocyanates having three or more isocyanate groups; and burette-type adducts and isocyanurate ring adducts of these polyisocyanates; and the like can be mentioned.

The hydroxyl value of the hydroxyl group-containing polyurethane resin is preferably in the range of 80 to 250 mgKOH / g, more preferably 100 to 200 mgKOH / g. The weight average molecular weight of the hydroxyl group-containing polyurethane resin is preferably in the range of 500 to 10000, more preferably 1000 to 5000.

As the binder component (A), a resin other than the hydroxyl group-containing acrylic resin (A1-1) and the hydroxyl group-containing acrylic resin (A1-1) (more specifically, a polyester resin, a polyurethane resin, a polyether resin, etc.) When used in combination, the content of the resin other than the hydroxyl group-containing acrylic resin (A1-1) is preferably 50 parts by mass or less with respect to 100 parts by mass of the solid content of the hydroxyl group-containing acrylic resin (A1-1). More preferably, it is in the range of 1 to 20 parts by mass.

Crosslinking agent (A2)
In the coating composition of the present invention, the binder component (A) can contain a cross-linking agent (A2). The cross-linking agent (A2) is a compound capable of reacting with a cross-linking functional group in the binder component (A), and is a compound capable of forming a cross-linked structure by the reaction. Among them, it is preferable that the crosslinkable functional group in the binder component (A) is a hydroxyl group and the crosslinking agent (A2) is a compound having reactivity with a hydroxyl group.

Specifically, as the cross-linking agent (A2), for example, a polyisocyanate compound, a blocked polyisocyanate compound, an amino resin, or the like can be preferably used. Among them, it is preferable that the cross-linking agent (A2) contains a polyisocyanate compound from the viewpoint of finished appearance, scratch resistance and the like.

The polyisocyanate compound is a compound having at least two isocyanate groups in one molecule, and is, for example, an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, an aromatic aliphatic polyisocyanate compound, or an aromatic polyisocyanate compound. , Derivatives of the polyisocyanate compound and the like.

Examples of the aliphatic polyisocyanate compound include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1, An aliphatic diisocyanate compound such as 3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, diisocyanate dimerate, methyl 2,6-diisocyanatohexanate (common name: lysine diisocyanate) 2-Isocyanatoethyl 2,6-diisocyanatohexanoate, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane , 1,8-Diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, etc. Isocyanate compounds and the like can be mentioned.

Examples of the alicyclic polyisocyanate compound include 1,3-cyclopentenediisocyanate, 1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate, and 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (conventional use). Name: Isophorone diisocyanate), 4-Methyl-1,3-cyclohexylene diisocyanate (common name: hydrogenated TDI), 2-methyl-1,3-cyclohexylene diisocyanate, 1,3- or 1,4-bis (isocyanate) Natomethyl) cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, methylenebis (4,1-cyclohexanediyl) diisocyanate (common name: hydrogenated MDI), alicyclic diisocyanate compounds such as norbornenan diisocyanate; 1,3 , 5-Triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 2- (3-Isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) ) -Bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 6- (2-Isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl- 2- (3-Isocyanatopropyl) -bicyclo (2.2.1) -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2) .2.1) Examples of alicyclic triisocyanate compounds such as heptane can be mentioned.

Examples of the aromatic aliphatic polyisocyanate compound include methylenebis (4,1-phenylene) diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω, ω'-diisocyanato. Aromatic aliphatic diisocyanate compounds such as -1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or a mixture thereof; , 3,5-Triisocyanatomethylbenzene and other aromatic aliphatic triisocyanate compounds and the like can be mentioned.

Examples of the aromatic polyisocyanate compound include m-phenylenediocyanate, p-phenylenediocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediocyanate, and 2,4-tolylene diisocyanate (common name: 2,4). -TDI) or 2,6-tolylene diisocyanate (common name: 2,6-TDI) or a mixture thereof, aromatic diisocyanate compounds such as 4,4'-toluene diisocyanate and 4,4'-diphenyl ether diisocyanate; triphenylmethane Aromatic triisocyanate compounds such as -4,4', 4''-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene; 4,4'-diphenylmethane-2 , 2', 5,5'-Aromatic tetraisocyanate compounds such as tetraisocyanate can be mentioned.

Examples of the derivative of the polyisocyanate compound include dimer, trimmer, biuret, allophanate, uretdione, uretoimine, isocyanurate, oxadiazine trione, and polymethylene polyphenyl polyisocyanate (crude MDI, polypeptide) of the above-mentioned polyisocyanate compound. MDI), crude TDI and the like can be mentioned.

The polyisocyanate compound and its derivative may be used alone or in combination of two or more.

As the polyisocyanate compound, it is preferable to use at least one selected from an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound and a derivative thereof from the viewpoint of weather resistance of the formed coating film and the like. It is more preferable to use an aliphatic polyisocyanate compound and / or a derivative thereof from the viewpoints of high solid differentiation of the coating composition to be obtained, the finished appearance of the formed coating film, scratch resistance, and the like.

The aliphatic polyisocyanate compound and / or a derivative thereof includes the aliphatic diisocyanate compound and / or the aliphatic diisocyanate compound from the viewpoints of high solid differentiation of the obtained coating composition, the finished appearance of the formed coating film, and scratch resistance. Alternatively, it is preferable to use an isocyanurate compound thereof, and it is more preferable to use hexamethylene diisocyanate and / or an isocyanurate compound thereof.

When the coating composition of the present invention contains the above polyisocyanate compound as the cross-linking agent (A2), the content ratio of the polyisocyanate compound is the above from the viewpoint of the finished appearance of the formed coating film, scratch resistance and the like. The range is preferably 5 to 60 parts by mass, more preferably 15 to 50 parts by mass, and further preferably 25 to 45 parts by mass, based on 100 parts by mass of the total solid content of the hydroxyl group-containing resin (A1) and the cross-linking agent (A2). Is inside.

Further, the blocked polyisocyanate compound that can be used as a cross-linking agent (A2) is a compound in which the isocyanate group of the polyisocyanate compound is blocked with a blocking agent.

Examples of the blocking agent include phenol-based agents such as phenol, cresol, xylenol, nitrophenol, ethylphenol, hydroxydiphenyl, butylphenol, isopropylphenol, nonylphenol, octylphenol, and methyl hydroxybenzoate; ε-caprolactam, δ-valerolactam, Oximes such as γ-butyrolactam and β-propiolactam; aliphatic alcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol and lauryl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Ether systems such as butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and methoxymethanol; benzyl alcohol, glycolic acid, methyl glycolate, ethyl glycolate, butyl glycolate, lactic acid, methyl lactate, ethyl lactate, lactic acid. Alcohols such as butyl, methylol urea, methylol melamine, diacetone alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate; formamide oxime, acetoamide oxime, acetooxime, methyl ethyl ketooxime, diacetylmonooxime, benzophenone oxime, cyclohexane oxime, etc. Oxime-based; active methylene-based such as dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylacetone; butyl mercaptan, t-butyl mercaptan, hexyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thio Mercaptans such as phenol, methylthiophenol, ethylthiophenol; acidamides such as acetoanilide, acetoaniside, acetotolide, acrylamide, methacrylicamide, acetateamide, stearate amide, benzamide; succinide imide, phthalateimide, maleateimide, etc. Imid-based; diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine, butylphenylamine and other amine-based; imidazole, 2-ethylimidazole and other imidazole-based; urea, thiourea , Ethyleneurea, ethylenethiourea, diphenyl Urea type such as urea; Carbamic acid ester type such as N-phenylcarbamic acid phenyl; Imine type such as ethyleneimine and propyleneimine; Sulfite type such as sodium bisulfite and potassium bisulfite; Azol type compound and the like. .. Examples of the azole compound include pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3, Pyrazole or pyrazole derivatives such as 5-dimethylpyrazole, 3-methyl-5-phenylpyrazole; imidazole or imidazole derivatives such as imidazole, benzimidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole; 2-methylimidazoline , 2-Pyrazole imidazoline and other imidazoline derivatives can be mentioned.

Among them, preferred blocking agents include oxime-based blocking agents, active methylene-based blocking agents, pyrazoles or pyrazole derivatives.

When blocking (reacting the blocking agent), a solvent can be added as needed. The solvent used for the blocking reaction may be one that is not reactive with the isocyanate group. For example, acetone, ketones such as methyl ethyl ketone, esters such as ethyl acetate, and N-methyl-2-pyrrolidone (NMP). Such solvents can be mentioned.

When the coating composition of the present invention contains the blocked polyisocyanate compound as the cross-linking agent (A2), the content ratio of the blocked polyisocyanate compound determines the finished appearance and scratch resistance of the formed coating film. From the viewpoint, the total solid content of the binder component is preferably in the range of 5 to 60 parts by mass, more preferably 15 to 50 parts by mass, and further preferably 25 to 45 parts by mass based on 100 parts by mass of the total solid content.

When the coating composition of the present invention contains the polyisocyanate compound and / or the blocked polyisocyanate compound as the cross-linking agent (A2), the blending ratio thereof is the water resistance of the formed coating film, the finished appearance, and the like. From the viewpoint of the above, the equivalent ratio (NCO / OH) of the total isocyanate group (including the blocked isocyanate group) of the polyisocyanate compound and the blocked polyisocyanate compound to the hydroxyl group of the hydroxyl group-containing resin (A1) is usually 0. It is preferable to use it at a ratio of 5 to 2, particularly 0.8 to 1.5.

As the amino resin that can be used as the cross-linking agent (A2), a partially methylolated amino resin or a completely methylolated amino resin obtained by the reaction of the amino component and the aldehyde component can be used. Examples of the amino component include melamine, urea, benzoguanamine, acetoguanamine, steloganamin, spiroguanamine, dicyandiamide and the like. Examples of the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.

Further, the methylol group of the above-mentioned methylolated amino resin, which is partially or completely etherified with an appropriate alcohol, can also be used. Examples of the alcohol used for etherification include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethylbutanol, 2-ethylhexanol and the like.

As the amino resin, a melamine resin is preferable. As the melamine resin, for example, an alkyl etherified melamine resin in which the methylol group of the partially or completely methylolated melamine resin is partially or completely etherified with the above alcohol can be used.

Examples of the alkyl etherified melamine resin include methyl etherified melamine resins obtained by partially or completely etherifying the methylol groups of the partially or fully methylolated melamine resin with methyl alcohol; the methylol groups of the partially or fully methylolated melamine resin. Butyl etherified melamine resin partially or completely etherified with butyl alcohol; methyl-butyl mixed etherification in which the methylol group of partially or completely methylolated melamine resin is partially or completely etherified with methyl alcohol and butyl alcohol. A melamine resin or the like can be preferably used.

The weight average molecular weight of the melamine resin is preferably in the range of 400 to 6000, more preferably 500 to 5000, and even more preferably 800 to 4000.

Commercially available products can be used as the melamine resin. Commercially available product names include, for example, "Symel 202", "Symel 203", "Symel 238", "Symel 251", "Symel 303", "Symel 323", "Symel 324", "Symel 325", "Symel 327", "Symel 350", "Symel 385", "Symel 1156", "Symel 1158", "Symel 1116", "Symel 1130" (all manufactured by Ornex Japan), "Uban 120", " Examples thereof include "Uban 20HS", "Uban 20SE60", "Uban 2021", "Uban 2028", and "Uban 28-60" (all manufactured by Mitsui Chemicals, Inc.).

The above-mentioned melamine resins can be used individually or in combination of two or more.

When the coating composition of the present invention contains the above amino resin as the cross-linking agent (A2), the blending ratio thereof is 100 in total solid content of the binder component from the viewpoint of water resistance of the formed coating film, finished appearance and the like. With reference to parts by mass, the range is preferably 0.5 to 40 parts by mass, more preferably 1.0 to 15 parts by mass, still more preferably 1.5 to 10 parts by mass, and particularly preferably 1.5 to 5 parts by mass. Is inside.

The above-mentioned cross-linking agent (A2) can be used alone or in combination of two or more.

Viscosity adjuster Generally, in a coating composition, the viscosity is low when the shear rate is high, such as when atomizing when painting (for example, by a coating method such as air spray coating, airless spray coating, or rotary atomization coating). When the shear rate is low as in the case of coating, it is preferable to use a paint having a high viscosity because a coating film having an excellent appearance can be formed. That is, it is preferable that the paint has a viscosity that decreases as the shear rate increases. The viscosity modifier refers to a component contained in the coating composition in order to develop a desired viscosity in this way.

First viscosity modifier (B)
The first viscosity modifier (B) is a non-aqueous dispersion resin (b).

The non-aqueous dispersion resin (b) exists in an insoluble state (opaque state) in the coating composition.

The non-aqueous dispersion resin (b) has a structure including a core portion and a shell portion.

The non-aqueous dispersion resin (b) is an acrylic resin particle (b3) obtained by dispersing and polymerizing at least one polymerizable unsaturated monomer (b2) in the presence of a polymer dispersion stabilizer (b1) and an organic solvent. Is preferable. Here, the polymer dispersion stabilizer (b1) serves as a shell portion, and acrylic resin particles (b3) formed by dispersion-polymerizing the polymerizable unsaturated monomer (b2) form a core portion.

As the polymer dispersion stabilizer (b1), a copolymer (b1-1) obtained by copolymerizing a long-chain unsaturated monomer with another unsaturated monomer, if necessary, can be preferably used.

The long-chain unsaturated monomer can be appropriately selected according to the performance required for the coating film, and the following are exemplified as long-chain unsaturated monomers that can be preferably used from the viewpoint of copolymerizability, solubility in organic solvents, and the like. can do.

For example, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth). Alkyl or cycloalkyl ester of (meth) acrylic acid having 4 to 18 carbon atoms such as acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate; methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxybutyl ( Alkoxyalkyl ester of (meth) acrylic acid such as meta) acrylate; ester of aromatic alcohol such as benzyl (meth) acrylate with (meth) acrylic acid; hydroxyalkyl ester of glycidyl (meth) acrylate or (meth) acrylic acid Acrylate with a monocarboxylic acid compound such as capric acid, lauric acid, linoleic acid, oleic acid; an addition of (meth) acrylic acid with a monoepoxy compound such as "Cajyura E10"; styrene, α-methylstyrene, Vinyl aromatic compounds such as vinyltoluene, p-chlorostyrene, pt-butylstyrene; (meth) acrylic acids such as itaconic acid, itaconic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, etc. Mono or diester compounds of α, β-unsaturated carboxylic acids other than butyl alcohol, butyl alcohol, pentyl alcohol, heptyl alcohol, octyl alcohol, stearyl alcohol and other mono alcohols having 4 to 18 carbon atoms; "Viscoat 8F", "Viscoat 8FM" , "Viscoat 3F", "Viscoat 3FM" (all manufactured by Osaka Organic Chemical Co., Ltd., trade name, (meth) acrylate compound having a fluorine atom in the side chain), perfluorocyclohexyl (meth) acrylate, perfluorohexyl Examples thereof include fluorine atom-containing compounds such as ethylene.

Among them, as the long-chain unsaturated monomer, an alkyl ester having 4 to 18 carbon atoms of (meth) acrylic acid is preferably used as at least one of them from the viewpoint of sagging resistance at the time of coating, and (meth). It is more preferable to use an alkyl ester having 6 to 18 carbon atoms of acrylic acid.

Specific examples of the alkyl ester having 4 to 18 carbon atoms of the (meth) acrylic acid include n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl. Examples thereof include (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and stearyl (meth) acrylate.

Specific examples of the alkyl ester having 6 to 18 carbon atoms of the (meth) acrylic acid include 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, and tridecyl. Examples thereof include (meth) acrylate and stearyl (meth) acrylate.

Among them, 2-ethylhexyl (meth) acrylate can be preferably used from the viewpoint of dispersion stability.

The unsaturated monomer other than the long-chain unsaturated monomer used as necessary for the polymerization of the copolymer (b1-1) may be an unsaturated monomer other than the long-chain unsaturated monomer as listed above. For example, the alkyl ester of (meth) acrylic acid having 1 to 3 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate; glycidyl (meth) acrylate and acetic acid is not particularly limited. , Additives with monocarboxylic acid compounds having 2-3 carbon atoms such as propionic acid; other than (meth) acrylic acids such as itaconic acid, itaconic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, etc. Α, β-unsaturated carboxylic acid and mono or diester compound with 1 to 3 carbon atoms such as methyl alcohol and propyl alcohol; cyano group-containing unsaturated compound such as (meth) acrylonitrile; vinyl acetate and the like. Vinyl ester compounds; vinyl ether compounds such as ethyl vinyl ether and methyl vinyl ether; α-olefin compounds such as ethylene, propylene, vinyl chloride and vinylidene chloride can be mentioned. Unsaturated monomers other than the long-chain unsaturated monomer also include those in which the unsaturated monomers listed above are replaced with hydroxyl groups or the like, such as 2-hydroxyethyl (meth) acrylate.

The polymerization for producing the above-mentioned copolymer (b1-1) can usually be carried out using a radical polymerization initiator. Examples of the radical polymerization initiator include azo-based initiators such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile); benzoyl peroxide, lauryl peroxide, and the like. Examples thereof include peroxide-based initiators such as t-butylperoctate and t-butylperoxy-2-ethylhexanoate, and these polymerization initiators are generally 0 per 100 parts by mass of a monomer to be polymerized. It can be used in the range of about 2 to 10 parts by mass, preferably 0.5 to 5 parts by mass. The reaction temperature during polymerization is usually about 60 to 160 ° C., and the reaction time during polymerization is usually about 1 to 15 hours.

The molecular weight of the copolymer (b1-1) is usually in the range of about 5,000 to 100,000, preferably about 5,000 to 50,000 in terms of weight average molecular weight. By using a copolymer having a molecular weight in the above range as a dispersion stabilizer, aggregation and sedimentation are suppressed by stabilizing dispersed particles, and a coating material that is not too viscous and easy to handle can be obtained, which is preferable.

The above-mentioned copolymer (b1-1) can be used alone or in combination of two or more. Further, as the polymer dispersion stabilizer (b1), other dispersion stabilizers (b1-2) other than the copolymer (b1-1) can be used, if necessary.

As the other dispersion stabilizer (b1-2), for example, those exemplified in the following (1) to (7) can be used.
(1) A polyester macromonomer in which a self-condensing polyester of a fatty acid containing a hydroxyl group such as a hydroxy acid and glycidyl acrylate or glycidyl methacrylate are added to introduce about 1.0 polymerizable unsaturated groups into the molecule.
(2) A comb-shaped polymer obtained by copolymerizing the polyester macromonomer of (1) above with methyl methacrylate and / or other (meth) acrylic acid ester or vinyl monomer.
(3) An unsaturated group is introduced by copolymerizing a small amount of glycidyl (meth) acrylate with the above (2) and then adding (meth) acrylic acid to the glycidyl group.
(4) Alkyl melamine resin.
(5) An alkyd resin having a fatty acid content of 15% or more and / or a product having a polymerizable unsaturated group introduced therein. Examples of the method for introducing the polymerizable unsaturated group include a method of adding glycidyl (meth) acrylate to the carboxyl group in the alkyd resin.
(6) An oil-free polyester resin, an alkyd resin having a fatty acid content of 15% or more, and / or a resin having a polymerizable unsaturated group introduced therein.
(7) Cellulose acetate butyrate having a polymerizable unsaturated group introduced therein. Examples of the method for introducing a polymerizable unsaturated group include a method for adding isocyanate ethyl methacrylate to cellulose acetate butyrate.

As the other dispersion stabilizer (b1-2), the dispersion stabilizer of (3) can be preferably used from the viewpoint of dispersion stability and storage stability, and the self-condensing polyester as a constituent component is A fatty acid having a hydroxyalkyl group having 10 to 25 carbon atoms in the alkyl chain can be preferably used. Among them, 12-hydroxystearic acid can be preferably used as the fatty acid from the viewpoint of dispersion stability. When the other dispersion stabilizer (b1-2) contains the fatty acid, the fatty acid content is 0.1 to 30.0 based on the total amount of the polymerizable unsaturated monomer components constituting the shell portion. The mass% is preferable, and 1.0 to 25.0 mass% is more preferable.

It is preferable to use a catalyst for the self-condensation of the above fatty acids. Examples of the catalyst include sulfuric acid, paratoluenesulfonic acid, methanesulfonic acid, hydrochloric acid, phosphoric acid and the like.

When the copolymer (b1-1) and other dispersion stabilizer (b1-2) are used in combination as the polymer dispersion stabilizer (b1), the blending ratio thereof is dispersion stability and sagging resistance during coating. From the viewpoint of the above, the mass ratio of the copolymer (b1-1) / other dispersion stabilizer (b1-2) is preferably 99/1 to 20/80, preferably 85/15 to 40/60. Is more preferable.

As the organic solvent used for the polymerization, the acrylic resin particles (b3) produced by the polymerization are substantially insoluble, but the polymer dispersion stabilizer (b1) and the polymerizable unsaturated monomer (b2) are used. On the other hand, an organic solvent which is a good solvent is included. Specific examples of such organic solvents include aliphatic hydrocarbon solvents such as hexane, heptane, and octane; benzene, toluene, xylene, "Swazole 1000" (manufactured by Cosmo Petroleum Co., Ltd., trade name, high boiling point petroleum solvent) and the like. Aromatic hydrocarbon solvents; alcohol solvents such as isopropanol, n-butanol, iso-butanol, 2-ethylhexanol; ether solvents such as cellosolve, butyl cellosolve, diethylene glycol monobutyl ether; methyl isobutyl ketone, diisobutyl ketone, methyl ethyl ketone, methyl Ketone solvents such as hexyl ketone and ethyl butyl ketone; ester solvents such as ethyl acetate, isobutyl acetate, amyl acetate and 2-ethylhexyl acetate can be mentioned. These organic solvents can be used alone or in combination of two or more.

As the polymerizable unsaturated monomer (b2), an unsaturated monomer having excellent polymerizable properties and having a smaller carbon number than the monomer used as the monomer component of the polymer dispersion stabilizer (b1) is used. However, it is preferable because it is easily formed as dispersed polymer particles.

Examples of such polymerizable unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. ) Acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate and other (meth) acrylic acids Alkyl or cycloalkyl ester having 1 to 18 carbon atoms; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like ( Monoesteride of meta) acrylic acid and divalent alcohol having 2 to 8 carbon atoms; alkoxyalkyl of (meth) acrylic acid such as methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate Ester; Ester of aromatic alcohol such as benzyl (meth) acrylate with (meth) acrylic acid; glycidyl (meth) acrylate and acetic acid, propionic acid, oleic acid, pt-butylbenzoic acid and the like having 2 to 18 carbon atoms. Additives with monocarboxylic acid compounds; Additives with (meth) acrylic acid and monoepoxy compounds such as "Cajyura E10"; styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, pt -Vinyl aromatic compounds such as butylstyrene; with α, β-unsaturated carboxylic acids other than (meth) acrylic acids such as itaconic acid, itaconic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid, and citraconic acid. Mono or diester compounds with monoalcolate having 1 to 18 carbon atoms such as methyl alcohol, butyl alcohol, hexyl alcohol, stearyl alcohol; "Viscoat 8F", "Viscoat 8FM", "Viscoat 3F", "Viscoat 3FM" (all) Made by Osaka Organic Chemical Co., Ltd., trade name, (meth) acrylate compound having a fluorine atom in the side chain), perfluorocyclohexyl (meth) acrylate, fluorine atom-containing compound such as perfluorohexylethylene; (meth) acrylonitrile, etc. Cyano group-containing unsaturated compound; vinyl acetate, vinyl benzoate, "VEOVA" (manufactured by Shell Co., Ltd.) ); Vinyl ether compounds such as n-butyl vinyl ether, ethyl vinyl ether, methyl vinyl ether; di (meth) acrylate of 1,6-hexanediol, tri (meth) acrylate of trimethylpropane, divinylbenzene and the like. Polyvinyl compounds; α-olefin compounds such as ethylene, propylene, vinyl chloride, and vinylidene chloride can be mentioned.

As described above, the polymerizable unsaturated monomer (b2) forming the acrylic resin particles (b3) is made by using a monomer having a smaller number of carbon atoms than the number of carbon atoms of the monomer component used in the polymer dispersion stabilizer (b1). Particle components can be stably formed, but from this viewpoint, (meth) acrylic acid ester compounds, vinyl aromatic compounds, (meth) acrylonitrile, and hydroxyl group-containing polymerizable unsaturated compounds having 8 or less carbon atoms, preferably 4 or less carbon atoms. It is preferable to contain a monomer, an acid group-containing polymerizable unsaturated monomer, and the like, and it is particularly preferable to contain a hydroxyethyl (meth) acrylic acid ester. When a hydroxyl group-containing polymerizable unsaturated monomer is contained as a constituent component of the core portion, the content of the hydroxyl group-containing polymerizable unsaturated monomer is the total amount of the polymerizable unsaturated monomer component constituting the non-aqueous dispersion resin. As a reference, 1 to 60% by mass is preferable, 10 to 55% by mass is more preferable, and 15 to 50% by mass is particularly preferable.

The polymerization of the polymerizable unsaturated monomer (b2) is usually carried out using a radical polymerization initiator. Examples of the radical polymerization initiator that can be used include azo-based initiators such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile); benzoyl peroxide and lauryl. Examples thereof include peroxide-based initiators such as peroxide, t-butylperoctate, and t-butylperoxy-2-ethylhexanoate, and these polymerization initiators are generally 100 parts by mass of a monomer to be subjected to polymerization. It can be used in the range of about 0.2 to 10 parts by mass, preferably 0.5 to 5 parts by mass.

The ratio of the polymer dispersion stabilizer (b1) and the polymerizable unsaturated monomer (b2) present during the polymerization is the mass ratio of the polymer dispersion stabilizer (b1) / the polymerizable unsaturated monomer (b2). It is preferably 10/90 to 60/40, and more preferably 20/80 to 50/50.

Further, the total concentration of the polymer dispersion stabilizer (b1) and the polymerizable unsaturated monomer (b2) in the organic solvent is usually about 30 to 70% by mass, preferably about 30 to 60% by mass.
The polymerization can be carried out by a method known per se, and the reaction temperature at the time of polymerization is usually about 60 to 160 ° C., and the reaction time at the time of polymerization is usually about 1 to 15 hours.

By carrying out the polymerization reaction as described above, the liquid phase is a polymer dispersion stabilizer (b1) dissolved in an organic solvent, and the solid phase is acrylic resin particles obtained by polymerizing a polymerizable unsaturated monomer (b2). A stable dispersion of the non-aqueous dispersion resin (b) according to (b3) can be obtained. The average particle size of the non-aqueous dispersion resin (b) is usually in the range of about 0.1 to 1.0 μm. By setting the average particle size of the non-aqueous dispersion resin (b) in the above range, the viscosity of the non-aqueous dispersion does not become too high, and the non-aqueous dispersion resin (b) swells or aggregates during storage of the paint. Is preferable because it can suppress.

The particle size of the non-aqueous dispersion resin (b) is measured by a "COOLTER N4 type submicron particle analyzer" (trade name, manufactured by Beckman Coulter).

In the production of the non-aqueous dispersion resin (b), it is preferable to improve the storage stability and mechanical properties by binding the polymer dispersion stabilizer (b1) and the acrylic resin particles (b3).

As a method for binding the polymer dispersion stabilizer (b1) and the acrylic resin particles (b3), for example, at the stage of producing the polymer dispersion stabilizer (b1) in advance, a hydroxyl group, an acid group, an acid anhydride group, and an epoxy A monomer component having a functional group such as a group, a methylol group, an isocyanate group, an amide group, or an amino group is copolymerized as a part of a monomer forming a polymer dispersion stabilizer (b1), and further acrylic resin particles (b3). ) Is formed as a part of the polymerizable unsaturated monomer (b2), which is a functional group such as a hydroxyl group, an acid group, an acid anhydride group, an epoxy group, a methylol group, an isocyanate group, an amide group or an amino group that reacts with the functional group. This can be done by using the monomer having. Examples of these combinations include isocyanate group and hydroxyl group, isocyanate group and methylol group, epoxy group and acid (anhydrous) group, epoxy group and amino group, isocyanate group and amide group, acid (anhydrous) group and hydroxyl group and the like. Can be done.

Examples of the monomer having such a functional group include α, β-ethylene-free substances such as (meth) acrylate, crotonic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, and citraconic acid. Saturated carboxylic acid; glycidyl group-containing compounds such as glycidyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-alkoxymethyl (meth) acrylamide, diacetone Carboxylic acid amide compounds such as acrylamide and N-methylol (meth) acrylamide; containing sulfonic acid amide groups such as p-styrene sulfonamide, N-methyl-p-styrene sulfonamide and N, N-dimethyl-p-styrene sulfonamide. Compounds; Amino group-containing compounds such as (meth) acrylate-t-butylaminoethyl; Condensations of 2-hydroxyethyl (meth) acrylate and phosphoric acid or phosphate ester compounds, glycidyl groups such as glycidyl (meth) acrylate A phosphate group-containing compound such as a glycidyl group of a compound having a phosphate or a phosphate ester compound added; a sulfonic acid group-containing compound such as 2-acrylamide-2-methyl-propanesulfonic acid; m-isopropenyl. Examples thereof include an equimolar addition of -α, α-dimethylbenzyl isocyanate, isophorone diisocyanate or tolylene diisocyanate and hydroxy (meth) acrylate, and an isocyanate group-containing compound such as isocyanoethyl methacrylate.

Further, as another method for binding the polymer dispersion stabilizer (b1) and the acrylic resin particles (b3), an unsaturated monomer is polymerized in the presence of the polymer dispersion stabilizer (b1) having a polymerizable double bond. It can be done by letting it.

For the introduction of the polymerizable double bond into the polymer dispersion stabilizer (b1), for example, an acid group-containing monomer such as carboxylic acid, phosphoric acid, or sulfonic acid is used as the copolymerization component of the acrylic resin particles (b3). This can be carried out by reacting this acid group with a glycidyl group-containing unsaturated monomer such as glycidyl (meth) acrylate or allyl glycidyl ether. On the contrary, it can also be carried out by containing a glycidyl group in the polymer dispersion stabilizer (b1) and reacting it with an acid group-containing unsaturated monomer.

In the reaction between the glycidyl group-containing monomer and the carboxylic acid group-containing unsaturated monomer, the epoxy group and the carboxylic acid group are usually smooth in the presence of a polymerization inhibitor without causing reaction problems such as gelation. It can be carried out under conditions that react with, and it is suitable to heat at 120 to 170 ° C. for 3 to 15 hours. In this reaction, an esterification reaction catalyst such as a tertiary amine such as dimethylaminoethanol, a quaternary ammonium salt such as tetraethylammonium bromide or tetrabutylammonium bromide can be used, and an inert organic solvent is used. You may.

Examples of the polymerization inhibitor include hydroxy compounds such as hydroquinone, hydroquinone monomethyl ether, pyrocatechol, and pt-butylcatechol; nitrobenzene, nitrobenzoic acid, o-, m- or p-dinitrobenzene, 2,4-. Nitro compounds such as dinitrotoluene, 2,4-dinitrophenol, trinitrobenzene, picric acid; quinone compounds such as p-benzoquinone, dichlorobenzoquinone, chloranyl, anthraquinone, phenanthroquinone; nitrosobenzene, nitroso-β-naphthol, etc. Examples thereof include radical polymerization inhibitors such as nitroso compounds, which can be used alone or in combination of two or more.

Further, as yet another method for binding the polymer dispersion stabilizer (b1) and the acrylic resin particles (b3), a functional group that does not react with the polymer dispersion stabilizer (b1) and the acrylic resin particles (b3). It can also be carried out by producing a non-aqueous dispersion liquid into which is introduced, and then reacting this with a binder that binds the two.

Specifically, for example, in the presence of a hydroxyl group-containing polymer dispersion stabilizer and an organic solvent, the hydroxyl group-containing unsaturated monomer is polymerized alone or as a mixture with other unsaturated monomers, and both are non-aqueous dispersion containing a hydroxyl group. After producing the liquid, it can be carried out by blending a polyisocyanate compound or the like and reacting at room temperature for several hours to several days and at about 60 to 100 ° C. for about 1 to 5 hours.

The polyisocyanate compound may be any compound having two or more isocyanate groups in the molecule, for example, aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, or hydrides thereof. An aliphatic diisocyanate such as hexamethylene diisocyanate, lysine diisocyanate, dimer acid (dimerse of tall oil fatty acid) diisocyanate; alicyclic diisocyanate such as isophorone diisocyanate can be mentioned.

In addition to the above, a combination of an acid group-containing polymer dispersion stabilizer (b1) and acrylic resin particles (b3) and a polyepoxide, an epoxy group-containing polymer dispersion stabilizer (b1) and acrylic resin particles ( The combination of b3) and a polycarboxylic acid, the polymer dispersion stabilizer (b1) containing an epoxy group or an isocyanate group, the acrylic resin particles (b3), and a polysulfide compound can also be used.

Examples of the polyepoxide include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, epoxy group-containing acrylic resin and the like; and examples of the polycarboxylic acid include adipic acid, sebatic acid, azelaic acid, isophthalic acid and the like; Examples of the polysulfide include pentamethylene disulfide, hexamethylene disulfide, and poly (ethylene disulfide).

As described above, the polymer dispersion stabilizer (b1) and the acrylic resin particles (b3) can be chemically bonded, and at this time, various functional groups and / or polymerizable double bonds are polymerized. The amount introduced into the dispersion stabilizer (b1) and / or the acrylic resin particles (b3) is at least 0 on average in one molecule of the polymer dispersion stabilizer (b1) and / or the acrylic resin particles (b3). The amount of one is sufficient.

The content ratio of the polymer dispersion stabilizer (b1) and the acrylic resin particles (b3) in the non-aqueous dispersion resin (b) is the polymer dispersion stabilizer (b1) / acrylic resin particles (b1) / acrylic resin particles (b1) from the viewpoint of storage stability. In terms of the mass ratio of b3), 90/10 to 10/90 is preferable, and 80/20 to 30/70 is more preferable.

The non-aqueous dispersion resin (b) thus obtained is excellent in storage stability and further formed because the polymer dispersion stabilizer (b1) and the acrylic resin particles (b3) are chemically bonded. The resulting coating film can exhibit excellent chemical and mechanical properties.

Second viscosity modifier (C)
The second viscosity modifier (C) has (c1) a polyisocyanate compound, (c2) a primary monoamine having a number average molecular weight of 300 or less, and (c3) two or more amino groups, and has a number average molecular weight. The compounding ratio of the polyether amine (c3) containing the reaction product of the polyether amine having a number of 1000 or more and less than 6000 and having the number average molecular weight of 1000 or more and less than 6000 is the total of the components (c1) to (c3). It is in the range of 10 to 30% by mass based on the amount.

Polyisocyanate compound (c1)
As the polyisocyanate compound (c1), for example, the polyisocyanate compound described in the explanation column of the cross-linking agent (A2) can be used. The polyisocyanate compounds may be used alone or in combination of two or more.

As the polyisocyanate compound (c1), an aliphatic polyisocyanate compound and / or a derivative thereof is preferable from the viewpoints of sagging resistance at the time of coating, water whitening resistance of the formed coating film, and finished appearance, and the aliphatic diisocyanate is preferable. Compounds and / or isocyanurates thereof are more preferred. Of these, hexamethylene diisocyanate and / or an isocyanurate form thereof is preferable, and hexamethylene diisocyanate is more preferable.

Primary monoamine (c2) with a number average molecular weight of 300 or less
Examples of the primary monoamine (c2) having a number average molecular weight of 300 or less include benzylamine, ethylamine, n-propylamine, sec-propylamine, n-butylamine, sec-butylamine, tert-butylamine, and n-pentylamine. , Α-Methylbutylamine, α-ethylpropylamine, β-ethylbutylamine, hexylamine, octylamine, 2-ethylhexylamine, n-decylamine, 1-aminooctadecane (stearylamine), cyclohexylamine, aniline, 2- (2) -Aminoethoxy) ethanol or the like can be used. The primary monoamine (c2) can be used alone or in combination of two or more.

The primary monoamine (c2) having a number average molecular weight of 300 or less includes a primary monoamine having a benzene ring from the viewpoints of sagging resistance during painting, water whitening resistance of the formed coating film, and finished appearance. Is preferable, and benzylamine is more preferable.

The number average molecular weight of the primary monoamine (c2) having a number average molecular weight of 300 or less is preferably 60 from the viewpoints of sagging resistance at the time of coating, water whitening resistance of the formed coating film, and finished appearance. It is in the range of ~ 300, more preferably 75 to 250, and even more preferably 90 to 150.

Polyetheramine (c3)
The polyether amine (c3) is a polyether having two or more ether bonds in one molecule, having two or more amino groups, and having a number average molecular weight of 1000 or more and less than 6000. ..

Among them, the number average molecular weight of the above-mentioned polyetheramine (c3) is preferably 1000 to 5000, more preferably 2000, from the viewpoints of sagging resistance at the time of coating, water whitening resistance of the formed coating film, and finished appearance. It is in the range of ~ 5000, more preferably 2000 ~ 4000.

Further, the above-mentioned polyether amine (c3) is preferably a primary amine from the viewpoints of sagging resistance at the time of coating, water whitening resistance of the formed coating film, and finished appearance.

The above-mentioned polyether amine (c3) has two or more amino groups. From the viewpoints of sagging resistance at the time of painting, water whitening resistance of the formed coating film, finished appearance, etc., it is more preferable that it is at least one amine selected from diamine and triamine, and among them, triamine is preferable. Especially preferable.

Therefore, the above-mentioned polyether amine (c3) is at least one selected from a primary diamine and a primary triamine from the viewpoints of sagging resistance at the time of coating, water whitening resistance of the formed coating film, and finished appearance. It is preferably an amine, more preferably a primary triamine. In the present invention, the primary diamine is an amine having _two -NH ₂ groups, and the primary triamine is an amine having three -NH ₂ groups.

As the polyether amine (c3), for example, an amine having a polyoxyalkylene group can be preferably used.

The amine having a polyoxyalkylene group has a polyoxyalkylene group represented by the following general formula (1) from the viewpoints of sagging resistance at the time of coating, water whitening resistance of the formed coating film, and finished appearance. Preferable is at least one amine compound selected from a diamine (c3-1) and a polyamine (c3-2) having a polyoxyalkylene group represented by the following general formula (4) and having three or more amino groups. Can be used.

In particular, polyamines having a polyoxyalkylene group and three or more amino groups (c3-2) from the viewpoints of sagging resistance during painting, water whitening resistance of the formed coating film, and finished appearance. ) Can be used particularly preferably.

Diamine having a polyoxyalkylene group (c3-1)
The diamine having a polyoxyalkylene group (c3-1) is a diamine having a polyoxyalkylene group represented by the following general formula (1).

[In the formula, R ³ represents an alkylene group having 2 to 6 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, and more preferably at least one alkylene group selected from an ethylene group, a propylene group and a tetramethylene group. , R ⁴ represents an alkylene group having 2 to 6 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, and more preferably at least one alkylene group selected from an ethylene group, a propylene group and a tetramethylene group. It represents an integer of 9 to 134, preferably 27 to 112, more preferably 27 to 89, and the n oxyalkylene units (OR ⁴ ) may be the same or different from each other. When the oxyalkylene units (OR ⁴ ) are different from each other, the addition form (polymerization form) of the oxyalkylene unit (OR ⁴ ) may be a random type or a block type. Good. ]
The diamine (c3-1) having a polyoxyalkylene group is more specifically a diamine having a polyoxyalkylene group represented by the following general formula (2).

[In the formula, c represents an integer of 16 to 102, preferably 33 to 85, and more preferably 33 to 68. ]
And / or a diamine having a polyoxyalkylene group represented by the following general formula (3)

[In the formula, d and f each represent an integer of 1 to 20, preferably 2 to 15, more preferably 2 to 10, and e is an integer of 12 to 60, preferably 15 to 50, still more preferably 25 to 45. And d + f is in the range of 2 to 40. Among them, d + f is preferably in the range of 4 to 30, more preferably 4 to 20, and even more preferably 4 to 8. ]
Can be preferably used.

Further, as the diamine (c3-1) having the polyoxyalkylene group, a commercially available product can be used. As commercially available products, for example, "JEFFAMINE D-2000" (number average molecular weight: 2000, c≈33 in the above general formula (2)), "JEFFAMINE D-4000" (number average molecular weight: 4000, the above general formula (2) ), C≈68), "JEFFAMINE ED-2003" (number average molecular weight: 2000, d + f≈6, e≈39 in the above general formula (3)), "ELASTAMINE RT-1000" (number average molecular weight: 1000), etc. Can be used.

Polyamine with polyoxyalkylene group (c3-2)
The polyamine having a polyoxyalkylene group (c3-2) is a polyamine having a polyoxyalkylene group represented by the following general formula (4) and having three or more amino groups.

[In the formula, R ⁵ represents a q-valent organic group having a carbon atom at the bonding site with the oxygen atom shown in the formula, preferably a q-valent hydrocarbon group, and R ⁶ is an alkylene having 2 to 6 carbon atoms. It represents a group, preferably an alkylene group having 2 to 4 carbon atoms, more preferably at least one alkylene group selected from an ethylene group, a propylene group and a tetramethylene group, and p is 4 to 45, preferably 10 to 40, and further. It preferably represents an integer of 15 to 30, q represents an integer of 3 or more, preferably 3 to 6, and more preferably 3 or 4. Further, the p oxyalkylene units (OR ⁶ ) may be the same as or different from each other. When the oxyalkylene units (OR ⁶ ) are different from each other, the addition form (polymerization form) of the oxyalkylene unit (OR ⁶ ) may be a random type or a block type. ]
And / or a triamine having a polyoxyalkylene group represented by the following general formula (5)

[In the formula, j, k and r each represent an integer of 5 to 60, preferably 10 to 50, more preferably 10 to 40. Among them, j + k + r is preferably in the range of 17 to 102, more preferably 33 to 86, and even more preferably 33 to 68. ]
Can be preferably used.

Further, as the polyamine (c3-3) having the polyoxyalkylene group, a commercially available product can be used. Examples of the commercially available product include "JEFFAMINE T-3000" (number average molecular weight: 3000, j + k + r≈50 in the above general formula (5)) and "JEFFAMINE T-5000" (number average molecular weight: 5000, above general formula (5). In 5), j + k + r≈85) and the like can be used.

Reaction method In the reaction of the polyisocyanate compound (c1), the primary monoamine (c2) having a number average molecular weight of 300 or less, and the polyether amine (c3), the components (c1) to (c3) are generally mixed. It can be carried out by any chosen method at higher temperatures if necessary. The reaction is preferably carried out at a temperature of 5 ° C to 80 ° C, preferably at a temperature of 10 ° C to 60 ° C.

By this reaction, the carbonyl of the polyisocyanate compound (c1) and the amines of the primary monoamine (c2) and the polyether amine (c3) having a number average molecular weight of 300 or less form a urea bond to form a crosslinked structure. ..

Further, the above components (c1) to (c3) can generally be mixed by any selected method. For example, a mixture of a primary monoamine (c2) and a polyether amine (c3) and a polyisocyanate compound (c1) are dropped in parallel into a reaction vessel, for example, a mixture of a primary monoamine (c2) and a polyether amine (c3). It can be mixed by a method such as adding a polyisocyanate compound (c1) to the mixture, and may be mixed in several steps if necessary. Further, the reaction of the above components (c1) to (c3) is preferably carried out in the presence of an organic solvent.

Examples of the organic solvent include aromatic solvents such as toluene, xylene and "Swazole 1000" (manufactured by Cosmo Petroleum Co., Ltd., trade name, high boiling point petroleum solvent); aliphatic solvents such as mineral spirit; ethyl acetate, Esters such as butyl acetate, propyl propionate, butyl propionate, 1-methoxy-2-propyl acetate, 2-ethoxyethyl propionate, 3-methoxybutyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, etc. Systems Solvents: Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and methyl amyl ketone, alcohol solvents such as isopropanol, n-butanol, isobutanol and 2-ethylhexanol and the like can be mentioned.

In the blending ratio of the components (c1) to (c3) when reacting the above components (c1) to (c3), the blending ratio of the polyether amine (c3) is the sagging resistance at the time of coating and the coating film formed. From the viewpoint of water whitening resistance of the film, finished appearance, and the like, the range is in the range of 10 to 30% by mass based on the total amount of the components (c1) to (c3).

Further, the blending ratio of the components (c1) to (c3) when reacting the above components (c1) to (c3) includes sagging resistance at the time of coating, water whitening resistance of the formed coating film, and finished appearance. From the viewpoint of the above, it is preferable that the total amount of the components (c1) to (c3) is within the following range based on the total amount.
Polyisocyanate compound (c1): 30 to 60% by mass, preferably 30 to 55% by mass, more preferably 30 to 45% by mass,
Primary monoamine (c2) having a number average molecular weight of 300 or less: 30 to 60% by mass, preferably 35 to 60% by mass, more preferably 35 to 55% by mass,
Polyetheramine (c3): 10 to 30% by mass, preferably greater than 15% by mass and 30% by mass or less, more preferably 18 to 28% by mass.

Further, the total number of amino groups in the primary monoamine (c2) and the polyether amine (c3) when reacting the components (c1) to (c3) is the number of isocyanate groups in the polyisocyanate compound (c1). The ratio (amino group / isocyanate group) to to is preferably 0.7 to 1.5, more preferably 0., from the viewpoints of sagging resistance at the time of coating, water whitening resistance of the formed coating film, and finished appearance. It is in the range of 9 to 1.1, more preferably 0.95 to 1.05.

In the present invention, the second viscosity modifier (C) is usually a polyisocyanate compound in addition to the reaction products of the polyisocyanate compound (c1), the primary monoamine (c2) and the polyetheramine (c3). It may contain reaction products of (c1) and primary monoamines (c2), and may further contain reaction products of polyisocyanate compound (c1) and polyetheramine (c3).

Further, the reaction of the above components (c1) to (c3) is preferably carried out in the presence of the resin component from the viewpoint of suppressing aggregation of the reaction product.

Examples of the resin component used for the reaction of the above components (c1) to (c3) include acrylic resin, polyester resin, polyether resin, polycarbonate resin, polyurethane resin, epoxy resin, alkyd resin, and the like. Acrylic resin can be preferably used from the viewpoints of sagging resistance at the time of coating, water whitening resistance of the coating film, finished appearance, and the like. The resin component may be a binder component (A), or may be a resin component different from the binder component (A). Preferably, a film-forming resin other than the acrylic resin (A1-1b) having the hydroxyl group and the alkoxysilyl group and the acrylic resin (A1-1c) having the secondary hydroxyl group and the alkoxysilyl group, for example, the secondary hydroxyl group-containing acrylic A resin (A1-1a) is used as the above resin component.

When the reaction of the above components (c1) to (c3) is carried out in the presence of the above resin component, the mixing ratio of the components (c1) to (c3) and the resin component is the same as that of the components (c1) to (c3). The ratio of the total mass to the mass of the resin component is the ratio of (total mass of components (c1) to (c3)) / (mass of resin component), preferably 1/99 to 15/85, more preferably 2 /. It is in the range of 98 to 12/88.

When the reaction of the above components (c1) to (c3) is carried out in the presence of the above resin component, the resin component shall not be included in the second viscosity modifier (C).

Paint Composition The paint composition of the present invention (hereinafter, may be abbreviated as "the present paint") includes the binder component (A), the first viscosity modifier (B), and the second viscosity modifier (C). ) Is a coating composition containing.

In the coating composition of the present invention, the content of the first viscosity modifier (B) is the above from the viewpoint of sagging resistance at the time of coating of the obtained coating composition and the finished appearance of the formed coating film. The total solid content of the binder component (A) and the first viscosity modifier (B) is preferably in the range of 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, based on 100 parts by mass.

In the coating composition of the present invention, the content of the second viscosity modifier (C) is the above-mentioned binder component (from the viewpoints of sagging resistance at the time of coating, water whitening resistance of the formed coating film, finished appearance, and the like. Based on 100 parts by mass of the total solid content of A) and the first viscosity modifier (B), preferably 0.05 to 1 part by mass, more preferably 0.1 to 0.9 parts by mass, still more preferably 0. It is in the range of .15 to 0.8 parts by mass.

The second reason why the coating composition of the present invention can form a coating film having excellent sagging resistance at the time of coating and excellent finished appearance and water whitening resistance of the formed coating film is as described above. It is mentioned that the viscosity adjusting agent (C) is used and the first viscosity adjusting agent (B) and the second viscosity adjusting agent (C) are used in combination.

The second viscosity modifier (C) has the polyisocyanate compound (c1), a primary monoamine (c2) having a number average molecular weight of 300 or less, two or more amino groups, and a number average molecular weight of 1000 or more. It is a reaction product of polyetheramine (c3) of less than 6000, and when it is included in the coating composition, it becomes a viscosity modifier having a fine crystal structure and forms a dense network in the coating composition. Since it exhibits the ability to suppress dripping, the sagging resistance during coating and the finished appearance of the obtained coating film are improved, and the fine crystal structure improves the solubility during coating film formation, resulting in water whitening resistance. It is presumed that an excellent coating film is formed.

Further, by using the first viscosity adjusting agent (B) and the second viscosity adjusting agent (C) in combination, two kinds of networks appearing in different temperature regions are formed in the coating composition and drips. It is presumed that the flowability is improved and the finished appearance is further improved while ensuring the suppressing ability.

The coating composition of the present invention may further contain a coloring pigment, a bright pigment, a dye and the like, if necessary, and further, an extender pigment, an ultraviolet absorber, a light stabilizer, a catalyst, an antifoaming agent, etc. A viscosity modifier, a rust preventive agent, a surface conditioner, an organic solvent, and the like other than the first viscosity modifier (B) and the second viscosity modifier (C) can be appropriately contained.

Examples of coloring pigments include titanium oxide, zinc flower, carbon black, cadmium red, molybdenum red, chromium yellow, chromium oxide, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, and slene pigment. Perylene pigment and the like can be mentioned.

Examples of the bright pigment include aluminum powder, mica powder, and mica powder coated with titanium oxide.

Examples of the extender pigment include talc, clay, kaolin, barita, barium sulfate, barium carbonate, calcium carbonate, alumina white and the like.

Each of the above pigments can be used alone or in combination of two or more.

When the coating composition of the present invention is used as a clear coating material and contains a pigment, the blending amount of the pigment is preferably an amount that does not impair the transparency of the obtained coating film, for example. It is preferably in the range of 0.1 to 20% by mass, more preferably 0.3 to 10% by mass, and particularly preferably 0.5 to 5% by mass with respect to the total amount of solids in the coating composition.

Further, when the coating composition of the present invention is used as a colored coating material and contains a pigment, the blending amount of the pigment is preferably 1 to 200% by mass with respect to the total amount of solid content in the coating composition. %, More preferably 2 to 100% by mass, and particularly preferably 5 to 50% by mass.

In the present specification, "solid content" means a non-volatile component such as a resin, a curing agent, or a pigment contained in the coating composition, which remains after the coating composition is dried at 110 ° C. for 1 hour. Therefore, for example, the total solid content of the coating composition is determined by weighing the coating composition in a heat-resistant container such as an aluminum foil cup, spreading the coating composition on the bottom surface of the container, and then drying at 110 ° C. for 1 hour. It can be calculated by weighing the masses of the components remaining in the coating composition after drying and obtaining the ratio of the masses of the components remaining after drying to the total mass of the coating composition before drying.

As the ultraviolet absorber, conventionally known ones can be used, and examples thereof include ultraviolet absorbers such as benzotriazole-based absorbents, triazine-based absorbents, salicylic acid derivative-based absorbents, and benzophenone-based absorbents. it can. These can be used alone or in combination of two or more.

When the coating composition of the present invention contains an ultraviolet absorber, the blending amount of the ultraviolet absorber is preferably 0.1 to 10% by mass, more preferably 0, based on the total amount of solids in the coating composition. It is in the range of 2 to 5% by mass, particularly preferably 0.3 to 2% by mass.

As the light stabilizer, conventionally known ones can be used, and examples thereof include hindered amine-based light stabilizers.

As the hindered amine-based light stabilizer, a hindered amine-based light stabilizer having low basicity can be preferably used from the viewpoint of pot life. Examples of such hindered amine-based light stabilizers include acylated hindered amines, amino ether-based hindered amines, and specifically, "HOSTAVIN 3058" (trade name, manufactured by Clariant), "TINUVIN 123" (trade name). , Made by BASF) and the like.

When the coating composition of the present invention contains a light stabilizer, the blending amount of the light stabilizer is preferably 0.1 to 10% by mass, more preferably 0, based on the total amount of solids in the coating composition. It is in the range of 2 to 5% by mass, particularly preferably 0.3 to 2% by mass.

As the catalyst, a conventionally known catalyst can be used. For example, when the coating composition of the present invention contains the polyisocyanate compound and / or the blocked polyisocyanate compound as the cross-linking agent (A2). The coating composition of the present invention can contain a urethanization reaction catalyst.

Specific examples of the urethanization reaction catalyst include tin octylate, dibutyltin diacetate, dibutyltin di (2-ethylhexanoate), dibutyltin dilaurate, dioctyltin diacetate, and dioctyltindi (2). -Ethylhexanoate), dibutyltin oxide, dibutyltin sulfide, dioctyltin oxide, dibutyltin fatty acid salt, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, fatty acid zincs, bismuth octanate, 2-ethyl Organic metal compounds such as bismuth hexane, bismuth oleate, bismuth neodecanoate, bismuth versaticate, bismuth naphthenate, cobalt naphthenate, calcium octylate, copper naphthenate, tetra (2-ethylhexyl) titanate; tertiary amines, etc. These can be used alone or in combination of two or more.

When the coating composition of the present invention contains the urethanization reaction catalyst, the blending amount of the urethanization reaction catalyst is preferably 0.005 to 2% by mass with respect to the total solid content of the coating composition of the present invention. , More preferably in the range of 0.01 to 1% by mass.

When the coating composition of the present invention contains the above-mentioned urethanization reaction catalyst, the coating composition of the present invention contains acetic acid, propionic acid, butyric acid, isopentanoic acid, hexanoic acid, etc. from the viewpoint of storage stability, curability and the like. 2-Ethylbutyric acid, naphthenic acid, octyl acid, nonanoic acid, decanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, versatic acid, Organic acids such as isobutyric anhydride, itaconic anhydride, acetic acid anhydride, citraconic anhydride, propionic anhydride, maleic anhydride, butyric anhydride, citric anhydride, trimellitic anhydride, pyromellitic anhydride, phthalic anhydride; hydrochloric acid, phosphorus Inorganic acids such as acids; metal coordinating compounds such as acetylacetone and imidazole compounds may be contained.

When the coating composition of the present invention uses the melamine resin as the cross-linking agent (A2), the coating composition of the present invention contains paratoluenesulfonic acid, dodecylbenzenesulfonic acid, and dinonylnaphthalenesulfonic acid as curing catalysts. Sulphonic acids such as: Monobutyl phosphate, dibutyl phosphate, mono (2-ethylhexyl) phosphate, alkyl phosphate such as di (2-ethylhexyl) phosphate; may contain salts of these acids and amine compounds. it can.

When the coating composition of the present invention contains the curing catalyst of the melamine resin, the blending amount of the curing catalyst of the melamine resin is preferably 0.1 to 2 with respect to the total solid content of the coating composition of the present invention. It is in the range of mass%, more preferably 0.2 to 1.7 mass%, still more preferably 0.3 to 1.4 mass%.

The object to be coated to which the coating composition of the present invention is applied is not particularly limited, and is, for example, an outer panel of an automobile body such as a passenger car, a truck, a motorcycle, or a bus; an automobile part; a mobile phone, an audio device. The outer panel portion of household electric products such as the above can be mentioned, and among them, the outer panel portion of the automobile body and the automobile parts are preferable.

The material of the object to be coated is not particularly limited, and for example, iron, aluminum, brass, copper, tin, stainless steel, zinc-plated steel, and alloyed zinc (Zn-Al, Zn-Ni, Zn-Fe, etc.) Metal materials such as plated steel; resins such as polyethylene resin, polypropylene resin, acrylonitrile-butadiene-styrene (ABS) resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin, epoxy resin, etc. And various plastic materials such as FRP; inorganic materials such as glass, cement and concrete; wood; fiber materials (paper, cloth, etc.), etc. Among them, metal materials and plastic materials are preferable.

The object to be coated may be a metal surface such as the metal material or a vehicle body formed from the metal material, which has been subjected to surface treatment such as phosphate treatment, chromate treatment, or composite oxide treatment. Further, the object to be coated may be a metal base material, a vehicle body, or the like on which an undercoat coating film such as various electrodeposition coating films is formed, and an intermediate coating film is formed on the undercoat coating film. It may be the one that has been done. Further, a primer coating film may be formed on a plastic base material such as a bumper.

The coating method of the coating material (hereinafter referred to as the present coating material) composed of the coating composition of the present invention is not particularly limited, and for example, air spray coating, airless spray coating, rotary atomization coating, curtain coat coating and the like. The coating method of the above can be mentioned, and a wet coating film can be formed by these methods. In these coating methods, static electricity may be applied if necessary. Of these, air spray coating or rotary atomization coating is particularly preferable. The coating amount of this coating material is usually an amount such that the cured film thickness is preferably 10 to 60 μm, more preferably 25 to 55 μm. Of these, 35 to 55 μm is preferable, and 41 to 50 μm is particularly preferable.

In addition, when performing air spray coating, airless spray coating, and rotary atomization coating, the viscosity of this coating material is set to a viscosity range suitable for the coating, usually Ford Cup No. 4 The viscometer is appropriately adjusted with a solvent such as an organic solvent so that the viscosity range is preferably 15 to 60 seconds, more preferably 20 to 40 seconds at 20 ° C.

The wet coating film formed by applying the present paint to the object to be coated can be cured by heating, and the heating can be performed by a known heating means, for example, a hot air furnace, an electric furnace, or an infrared induction heating. A drying furnace such as a furnace can be used. The heating temperature is not particularly limited and is, for example, in the range of 60 to 160 ° C, preferably 80 to 140 ° C. The heating time is not particularly limited and is, for example, in the range of 10 to 60 minutes, preferably 15 to 30 minutes.

Since this paint is a paint composition capable of forming a coating film having excellent water whitening resistance and finished appearance, it can be particularly preferably used as a top coat top clear coat paint. This paint can be particularly preferably used as a paint for automobiles.

Multi-layer coating film forming method As a multi-layer coating film forming method in which this paint is applied as a top coat top clear coat paint, at least one layer of colored base coat paint and at least one layer of clear coat paint are sequentially applied to an object to be coated. This is a method for forming a multi-layer coating film, and examples thereof include a method for forming a multi-layer coating film including coating the coating composition of the present invention as the clear coat coating material for the uppermost layer.

Specifically, for example, a colored base coat paint is applied onto an object to be coated by electrodeposition coating and / or an intermediate coating, and the colored base coat paint is used as necessary without curing the coating film. In order to promote the volatilization of the solvent, for example, preheating is performed at 40 to 90 ° C. for about 3 to 30 minutes, and the present paint is applied as a clear coat paint on the uncured colored base coat coating material. Examples thereof include a two-coat, one-bake method for forming a multi-layer coating film in which a colored base coating coating film and a clear coating coating film are cured together.

Further, this paint can also be suitably used as a top clear coat paint in the top coat coating of the 3-coat 2-bake method or the 3-coat 1-bake method.

As the base coat paint used above, a conventionally known ordinary thermosetting base coat paint can be used, and specifically, for a base resin such as an acrylic resin, a polyester resin, an alkyd resin, or a urethane resin. A coating material obtained by appropriately combining a cross-linking agent such as an amino resin, a polyisocyanate compound, or a blocked polyisocyanate compound with a reactive functional group contained in the base resin can be used.

Further, as the base coat paint, for example, a water-based paint, an organic solvent-based paint, or a powder paint can be used. Of these, water-based paints are preferable from the viewpoint of reducing the environmental load and the finished appearance of the coating film.

In the above multi-layer coating film forming method, when two or more layers of clear coat are applied, this paint may be used as the clear coat paint other than the uppermost layer, and a conventionally known thermosetting clear coat paint is used. You may.

Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples. However, the present invention is not limited thereto. In each example, "parts" and "%" are based on mass unless otherwise specified. The film thickness of the coating film is based on the cured coating film.

Production Example 1 of Production of Hydroxy Group-Containing Acrylic Resin (A1-1-1)
27 parts of "Swazole 1000" (trade name, manufactured by Cosmo Petroleum Co., Ltd., aromatic organic solvent) and propylene glycol monomethyl in a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, a nitrogen introduction tube and a dropping device. 5 parts of ether acetate was charged and stirred at 150 ° C. while blowing nitrogen gas, and 20 parts of styrene, 32.5 parts of 2-hydroxypropyl acrylate, 46.5 parts of isobutyl methacrylate, 1.0 part of acrylic acid and jitter were added therein. A monomer mixture consisting of 1.5 parts of shariamil peroxide (polymerization initiator) was added dropwise at a uniform rate over 4 hours. Then, it was aged at 150 ° C. for 1 hour and then cooled, and 34 parts of butyl acetate was added to dilute it to obtain a hydroxyl group-containing acrylic resin (A1-1-1) solution having a solid content concentration of 60% by mass. The obtained hydroxyl group-containing acrylic resin (A1-1-1) had a hydroxyl value of 140 mgKOH / g, an acid value of 8.0 mgKOH / g, a weight average molecular weight of 10,000, and a glass transition temperature of 39 ° C.

Production Example 2 of Production of Hydroxy Group-Containing Acrylic Resin (A1-1-2)
30 parts of "Swazole 1000" (trade name, manufactured by Cosmo Petroleum Co., Ltd., aromatic organic solvent) and n-butanol in a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, a nitrogen introduction tube and a dropping device. I prepared 10 copies. While blowing nitrogen gas into the reaction vessel, the charged liquid was stirred at 125 ° C., and 30 parts of γ-methacryloxypropyltrimethoxysilane, 32.5 parts of 2-hydroxypropyl acrylate, 20 parts of styrene, and 17.5 parts of isobutyl methacrylate were mixed therein. A monomer mixture consisting of parts and 7.0 parts of 2,2'-azobis (2-methylbutyronitrile) (polymerization initiator) was added dropwise at a uniform rate over 4 hours. Then, after aging at 125 ° C. for 30 minutes, 0.5 part of 2,2'-azobis (2-methylbutyronitrile) and "Swazole 1000" (trade name, manufactured by Cosmo Oil Co., Ltd., aromatic organic solvent) A solution consisting of 5.0 parts was added dropwise at a uniform rate over 1 hour. Then, it was aged at 125 ° C. for 1 hour, cooled, and further diluted by adding 8 parts of isobutyl acetate, and a hydroxyl group-containing acrylic resin (A1-1-2) solution (secondary hydroxyl group and alkoxy) having a solid content concentration of 65% by mass was added. Acrylic resin solution having a silyl group) was obtained. The obtained hydroxyl group-containing acrylic resin (A1-1-2) had an alkoxysilyl group content of 1.21 mmol / g, a hydroxyl value of 140 mgKOH / g, a weight average molecular weight of 7,000, and a glass transition temperature of 18 ° C.

Production Example 3 of Production of Hydroxy Group-Containing Acrylic Resin (A1-1-3)
30 parts of "Swazole 1000" (trade name, manufactured by Cosmo Petroleum Co., Ltd., aromatic organic solvent) and n-butanol in a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, a nitrogen introduction tube and a dropping device. I prepared 10 copies. The preparation liquid was stirred at 125 ° C. while blowing nitrogen gas into the reaction vessel, and 30 parts of γ-methacryloxypropyltrimethoxysilane, 32.5 parts of 2-hydroxyethyl methacrylate, 20 parts of styrene, and 17.5 parts of isobutyl methacrylate were mixed therein. A monomer mixture consisting of parts and 7.0 parts of 2,2'-azobis (2-methylbutyronitrile) (polymerization initiator) was added dropwise at a uniform rate over 4 hours. Then, after aging at 125 ° C. for 30 minutes, 0.5 part of 2,2'-azobis (2-methylbutyronitrile) and "Swazole 1000" (trade name, manufactured by Cosmo Oil Co., Ltd., aromatic organic solvent) A solution consisting of 5.0 parts was added dropwise at a uniform rate over 1 hour. Then, it is aged at 125 ° C. for 1 hour, cooled, and further diluted by adding 8 parts of isobutyl acetate to a hydroxyl group-containing acrylic resin (A1-1-3) solution having a solid content concentration of 65% by mass (primary hydroxyl group and alkoxy). Acrylic resin solution having a silyl group) was obtained. The obtained hydroxyl group-containing acrylic resin (A1-1-3) had an alkoxysilyl group content of 1.21 mmol / g, a hydroxyl value of 140 mgKOH / g, a weight average molecular weight of 7,000, and a glass transition temperature of 39 ° C.

Production of First Viscosity Adjusting Agent (B) Production Example 4
37 parts of heptane and 70 parts of "Swazole 1000" (trade name, manufactured by Cosmo Petroleum Co., Ltd., aromatic organic solvent) are charged into a four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen gas inlet to charge nitrogen. The temperature was raised to 100 ° C. while blowing. Next, 49.6 parts of the following copolymer dispersion stabilizer (b1-1-1) solution (Note 1), 10.5 parts of the following other dispersion stabilizer (b1-2-1) solution (Note 2), and the following. A mixture of 65.0 parts of the core monomer composition (Note 3), 0.9 parts of 2,2'-azobisisobutyronitrile, and 20 parts of "Swazole 1000" is added dropwise over 3 hours and aged for another 2 hours. As a result, a non-aqueous dispersion resin (b-1) solution was obtained. The obtained non-aqueous dispersion resin (b-1) solution had a solid content of 40% and an average particle size of 146 nm. The copolymer dispersion stabilizer (b1-1-1) / other dispersion stabilizer (b1-2-1) ratio was 85/15, and the core / shell ratio was 65/35.

(Note 1) Copolymer dispersion stabilizer (b1-1-1) solution In a four-necked flask equipped with a stirrer, thermometer, water separator, and nitrogen gas inlet, "Swazole 1000" (trade name, Cosmo) Twelve parts of an aromatic organic solvent manufactured by Cosmo Oil Co., Ltd. were charged and the temperature was raised to 125 ° C. Then, 8.8 parts of isobutyl methacrylate, 8.8 parts of 2-ethylhexyl acrylate, 8.8 parts of glycidyl methacrylate, 2.9 parts of 2-hydroxyethyl acrylate and 1.5 parts of t-butylperoxy-2-ethylhexanoate. A mixture of 4 parts and 4 parts of n-butanol was added dropwise over 4 hours and aged for another 1 hour. Then, a mixture of 0.15 part of t-butylperoxy-2-ethylhexanoate and 3 parts of "Swazole 1000" was added dropwise over 1 hour, and the mixture was further aged for 2 hours. Then, 0.02 part of pt-butylcatechol and 0.27 part of acrylic acid were added to the flask, and the reaction was continued for about 4 hours until the resin acid value became 1.0 or less, and the copolymer having a solid content of 60% was continued. A dispersion stabilizer (b1-1-1) solution was obtained.

(Note 2) Other dispersion stabilizer (b1-2-1) solution In a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet, under reflux with toluene, methanesulfonic acid is used as a catalyst. -Hydroxystearic acid was dehydrated and condensed to a resin acid value of 30. A polymerizable unsaturated group was introduced by adding glycidyl methacrylate using dimethylaminoethanol as a catalyst to the terminal carboxyl group of the obtained self-condensed polyester having a number average molecular weight of about 1800, and containing a polymerizable unsaturated group having a solid content of 70%. A macromonomer solution was obtained. The obtained polymerizable unsaturated group-containing macromonomer had about 1 polymerizable unsaturated group based on the number average molecular weight per molecule. Next, 2.7 parts of butyl acetate was placed in a flask and refluxed by heating. In this, 3.7 parts of the above 70% polymerizable unsaturated group-containing macromonomer solution, 2.4 parts of methyl methacrylate, and 0. A mixture of 2 parts, 2.5 parts of xylene and 0.15 parts of 2,2'-azobisisobutyronitrile was added dropwise at a uniform rate over 3 hours and aged for another 2 hours. Then, a mixture of 0.01 part of pt-butylcatechol, 0.05 part of methacrylic acid and 0.01 part of dimethylaminoethanol was added to the flask, and the resin acid value became 0.5 at 140 ° C. for about 5 hours. The reaction was continued to obtain a solution of another dispersion stabilizer (b1-2-1) having a solid content of 50%. The other dispersion stabilizer (b1-2-1) obtained was a graft polymer having a segment of 12-hydroxystearic acid and a segment of a copolymer of methyl methacrylate and glycidyl methacrylate, and was averaged in one molecule. It has about 4 polymerizable unsaturated groups.

(Note 3) Core monomer composition 6.5 parts of styrene, 15.6 parts of methyl methacrylate, 6.5 parts of methyl acrylate, 32.5 parts of 2-hydroxyethyl acrylate, 2.6 parts of glycidyl methacrylate, and 1. A mixture of three parts.

Production Examples 5 to 6
Non-aqueous dispersion resin (b-2) to (b-3) solutions were obtained in the same manner as in Production Example 4 except that the compounding composition was as shown in Table 1 in Production Example 4. The compounding composition shown in Table 1 depends on the solid content mass of each component.

Production Example 7 of Production of Second Viscosity Adjusting Agent (C)
In a reaction vessel equipped with a stirrer and a dropping device, 158.3 parts (solid content 95.0 parts) of the hydroxyl group-containing acrylic resin (A1-1-1) solution obtained in Production Example 1 and "Swazole 1000" (trade name). , Cosmo Petroleum Co., Ltd., aromatic organic solvent) 15.2 parts and n-butanol 10 parts were charged, and while stirring at room temperature, 2.44 parts of benzylamine and "JEFFAMINE D-2000" (trade name, HUNTSMAN) A diamine having a polyoxypropylene group and an amine mixture consisting of 0.6 parts of a number average molecular weight of 2000) were added. Next, a mixture of 1.96 parts of hexamethylene diisocyanate and 11.5 parts of "Swazole 1000" (trade name, manufactured by Cosmo Oil Co., Ltd., aromatic organic solvent) was added dropwise with stirring to disperse the second viscosity modifier. A liquid (CM-1) was obtained. The solid content of the obtained second viscosity modifier dispersion (CM-1) was 50%. Further, in the obtained second viscosity modifier dispersion liquid (CM-1), the total mass of the components (c1) to (c3) is 5.0 parts by mass, and the hydroxyl group-containing acrylic resin (resin component). The mass of A1-1-1) was 95.0 parts by mass, and the ratio of (total mass of components (c1) to (c3)) / (mass of resin component) was 5/95.

Production Examples 8 to 21
Second viscosity modifier dispersions (CM-2) to (CM-15) were obtained in the same manner as in Production Example 7 except that the compounding composition was as shown in Table 2 in Production Example 7. The solid content of the obtained second viscosity modifier dispersions (CM-2) to (CM-15) was 50%. The compounding composition shown in Table 2 depends on the solid content mass of each component.

(Note) in Table 2 means the following.

(Note 4) "JEFFAMINE T-3000": Trade name, manufactured by HUNTSMAN, triamine having a polyoxyalkylene group, number average molecular weight 3000.

(Note 5) "JEFFAMINE T-5000": Trade name, manufactured by HUNTSMAN, triamine having a polyoxyalkylene group, number average molecular weight 5000.

(Note 6) "JEFFAMINE M-1000": Product name, manufactured by HUNTSMAN, monoamine having a polyoxyalkylene group, number average molecular weight 1000.

(Note 7) "JEFFAMINE T-403": Trade name, manufactured by HUNTSMAN, triamine having a polyoxyalkylene group, number average molecular weight 440.

(Note 8) "JEFFAMINE D-400": Trade name, manufactured by HUNTSMAN, diamine having a polyoxyalkylene group, number average molecular weight 400.

Manufacture of paint composition 1
Example 1
82.3 parts (solid content 49.4 parts) of the hydroxyl group-containing acrylic resin (A1-1-1) solution obtained in Production Example 1, "Uban 20SE60" (trade name, manufactured by Mitsui Chemicals, Inc., melamine resin, containing solid content) (Ratio 60%) 6.7 parts (solid content 4 parts), 10 parts of the non-aqueous dispersion resin (b-1) solution obtained in Production Example 4 (solid content 4 parts), the third obtained in Production Example 7. 16 parts of the viscosity modifier dispersion solution (CM-1) solution (solid content is 8 parts, of which 0.4 parts is the second viscosity modifier (C) component, hydroxyl group-containing acrylic resin (A1-1) -1) is 7.6 parts), "BYK-300" (trade name, manufactured by Big Chemie, surface conditioner, active ingredient 52%) 0.4 parts (solid content 0.2 parts) and "NACURE 5523" (Product name, amine salt of dodecylbenzene sulfonic acid, catalyst, active ingredient 35%, manufactured by KING INDUSTRIES) 0.3 parts (solid content 0.1 parts) was uniformly mixed with the main agent.
Immediately before painting with 35 parts of "Sumijour N3300" (trade name, manufactured by Sumika Cobestrourethane, isocyanurate of hexamethylene diisocyanate, solid content 100%) which is a curing agent (crosslinking agent (A2)). Mix uniformly, and then add butyl acetate to No. Ford Cup No. at 20 ° C. Adjusting the viscosity according to No. 4 to 30 seconds, the coating composition No. I got 1.

Examples 2 to 21 and Comparative Examples 1 to 8
Ford Cup No. at 20 ° C. in the same manner as in Example 1 except that the compounding composition is as shown in Table 3 below. Each coating composition No. 4 having a viscosity of 30 seconds according to No. 4 2-29 were obtained. The compounding composition shown in Table 3 depends on the solid content mass of each component.

Preparation of test plate 1
Manufacture of test plates of Examples 1 to 21 and Comparative Examples 1 to 8 Preparation of test plates for finish appearance evaluation and water whitening resistance evaluation Cold spreading with a size of 10 cm × 15 cm and subjected to zinc phosphate chemical conversion treatment. "Electron GT-10" (trade name, manufactured by Kansai Paint Co., Ltd., cationic electrodeposition coating) is electrodeposited on the steel plate so that the dry film thickness is 20 μm, heated at 170 ° C. for 30 minutes to cure, and then cured. On the electrodeposition coating film, "WP-306T" (trade name, manufactured by Kansai Paint Co., Ltd., polyester melamine resin-based water-based intermediate coating paint) was applied to a cured film thickness of 30 μm using a rotary atomization type electrostatic coating machine. After electrostatic coating was performed for 5 minutes, preheating was performed at 80 ° C. for 3 minutes, and then heating was performed at 140 ° C. for 30 minutes to obtain a test object to be coated. Next, in a vertical state, "WBC-713T No. 202" (trade name, manufactured by Kansai Paint Co., Ltd., acrylic melamine resin-based water-based base coat paint, black paint color) was applied to the test object to be tested in a rotary atomization type. Using an electrostatic coating machine, electrostatic coating was performed so that the cured film thickness was 15 μm, and after leaving for 5 minutes, preheating was performed at 80 ° C. for 3 minutes in a vertical state. Next, on the uncured base coat coating film, in a vertical state, the coating composition No. 1 was electrostatically coated using a rotary atomization type electrostatic coating machine so as to have a dry film thickness of 45 μm to form a clear coat coating film, and left for 7 minutes. Next, the test plate of Example 1 was prepared by heating at 140 ° C. for 30 minutes (keeping time) in a vertical state to heat-cure the base coat coating film and the clear coat coating film.

The above paint composition No. In the preparation of the test plate of No. 1, the coating composition was designated as No. 1. Paint composition No. 2 except for any of 2 to 29. In the same manner as in the preparation of the test plate of No. 1, the coating composition No. 2 to 29 test plates were prepared respectively.

Preparation of test plate for sagging resistance evaluation "Electron GT-10" (trade name, manufactured by Kansai Paint Co., Ltd., cationic electrodeposition) on a cold-rolled steel plate with a size of 11 cm x 45 cm and subjected to zinc phosphate chemical conversion treatment. (Paint) is electrodeposited to a dry film thickness of 20 μm, heated at 170 ° C. for 30 minutes to cure, and then “WP-306T” (trade name, manufactured by Kansai Paint Co., Ltd.) is applied onto the electrodeposited coating film. Polyester melamine resin-based water-based intermediate coating paint) is electrostatically coated using a rotary atomization type electrostatic coating machine so that the cured film thickness is 30 μm, left for 5 minutes, and then preheated at 80 ° C. for 3 minutes. After that, it was heated at 140 ° C. for 30 minutes to obtain a test object to be coated. Next, 21 punch holes having a diameter of 5 mm are provided in a row at a portion 3 cm from the long end of the test object to be tested, as if it were 2 cm. In the vertical state, apply "WBC-713T No. 202" (trade name, manufactured by Kansai Paint Co., Ltd., acrylic melamine resin-based water-based base coat paint, black paint color) to a cured film using a rotary atomization type electrostatic coating machine. It was electrostatically coated so as to have a thickness of 15 μm, left for 5 minutes, and then preheated at 80 ° C. for 3 minutes in a vertical state. Next, on the uncured coating film, in a vertical state, the coating composition No. 1 was coated using a rotary atomization type electrostatic coating machine with a film thickness gradient so as to obtain a film thickness of approximately 30 μm to 60 μm in the long direction, and left at room temperature for 7 minutes. The test plate of Example 1 was prepared by heating the base coat coating film and the clear coat coating film at 140 ° C. for 30 minutes (keeping time) in a vertical state.

The above paint composition No. In the preparation of the test plate of No. 1, the coating composition was designated as No. 1. Paint composition No. 2 except for any of 2 to 29. In the same manner as in the preparation of the test plate of No. 1, the coating composition No. 2 to 29 test plates were prepared respectively.

Each of the test plates obtained above was evaluated by the following test method. The evaluation results are shown in Table 3 together with the coating composition.
(Test method)
Finished appearance: For each test plate, the finished appearance was evaluated based on the Long Wave (LW) value measured by "Wave Scan" (trade name, manufactured by BYK Gardener). The smaller the LW value, the higher the smoothness of the coated surface.

Water whitening resistance: Water whitening resistance is evaluated for each test plate based on the difference in L ^* values before and after immersion in warm water measured by "CM-512m3" (trade name, manufactured by Konica Minolta, multi-angle spectrophotometer). did. In this test, the L ^* value is calculated from three angles of 25 ° (highlight direction), 45 °, and 75 ° (shade direction) with respect to the light receiving angle (the direction perpendicular to the coated surface is 0 °). It is a total value of each L ^* value when each is irradiated with standard light D65. After measuring the L ^* value, 40 ° C. warm water was immersed in 10 days, by measuring the L ^* value of after immersion of the test plate, the difference between the L ^* value after immersing the L ^* value before immersion ΔL ^* Was calculated. The smaller ΔL ^* , the less whitening of the coating film due to immersion in warm water, and the higher the water whitening resistance.

Sauce resistance: For each test plate, the position where sagging of the coating film 3 mm is observed from the lower end of the punch hole is investigated, and the film thickness (sauce limit film thickness (μm)) at that position is measured to perform sagging resistance. Gender was evaluated. The larger the sagging limit film thickness, the better the sagging resistance.

Note that (Note) in Table 3 means the following.
(Note 9) "TINUVIN 400": Trade name, benzotriazole-based UV absorber, 100% active ingredient, manufactured by BASF.
(Note 10) "HOSTAVIN 3058": Trade name, hindered amine-based light stabilizer, acylated hindered amine, 100% active ingredient, manufactured by CLARIANT.
(Note 11) "NACURE 4167": Trade name, triethylamine salt of alkyl phosphoric acid, curing catalyst of melamine resin, 25% active ingredient, manufactured by KING INDUSTRIES.
(Note 12) "Neostan U-600": Product name, inorganic bismuth, 100% active ingredient, manufactured by Nitto Kasei.

Manufacture of paint composition 2
Example 22
32.3 parts (solid content 19.4 parts) of the hydroxyl group-containing acrylic resin (A1-1-1) solution obtained in Production Example 1, 33 parts of the hydroxyl group-containing acrylic resin (A1-1-2) solution obtained in Production Example 2. .8 parts (22 parts of solid content), "Uban 20SE60" (trade name, manufactured by Mitsui Chemicals, Inc., melamine resin, solid content content 60%) 6.7 parts (4 parts of solid content), obtained in Production Example 4. 10 parts (4 parts solid content) of the non-aqueous dispersion resin (b-1) solution, 32 parts (16 parts solid content) of the second viscosity modifier dispersion (CM-6) solution obtained in Production Example 12. Of these, 0.4 parts of the second viscosity modifier (C) component and 15.6 parts of the hydroxyl group-containing acrylic resin (A1-1-1)), "BYK-300" (trade name, trade name, Made by Big Chemie, surface conditioner, active ingredient 52%) 0.4 parts (solid content 0.2 parts) and "NACURE 5523" (trade name, amine salt of dodecylbenzene sulfonic acid, catalyst, active ingredient 35%, KING INDUSTRIES) 0.3 parts (0.1 parts solid content) of the main agent mixed uniformly,
Immediately before painting with 35 parts of "Sumijour N3300" (trade name, manufactured by Sumika Cobestrourethane, isocyanurate of hexamethylene diisocyanate, solid content 100%) which is a curing agent (crosslinking agent (A2)). Mix uniformly, and then add butyl acetate to No. Ford Cup No. at 20 ° C. Adjusting the viscosity according to No. 4 to 30 seconds, the coating composition No. I got 30.

Examples 23 to 24 and Comparative Example 9
Ford Cup No. at 20 ° C. in the same manner as in Example 22 except that the compounding composition is as shown in Table 4 below. Each coating composition No. 4 having a viscosity of 30 seconds according to No. 4 31-33 were obtained. The compounding composition shown in Table 4 depends on the solid content mass of each component.

Preparation of test plate 2
Production of test plates of Examples 22 to 24 and Comparative Example 9 Preparation of test plates for finish appearance evaluation, water whitening resistance evaluation and scratch resistance evaluation Test plate preparation 1 finished appearance evaluation and water whitening resistance evaluation In the preparation of the test plate for use, the coating composition was No. In the same manner as in Preparation 1 of the test plate, except that it is set to any of 30 to 33, the coating composition No. 30 to 33 test plates were prepared respectively.

Preparation of test plate for sagging resistance evaluation In the preparation of the test plate for sagging resistance evaluation in Production of Test Plate 1, the coating composition was No. In the same manner as in Preparation 1 of the test plate, except that it is set to any of 30 to 33, the coating composition No. 30 to 33 test plates were prepared respectively.

Each of the test plates obtained above was evaluated by the following test method. The evaluation results are shown in Table 4 together with the coating composition.
(Test method 2)
The finished appearance, water whitening resistance, and sagging resistance were the same as those in Test Method 1 above.

Scratch resistance: 20 degree mirror reflectance (20 degrees) of the test plate after washing the car with each test plate attached to the roof with Nichiban water resistant tape 15 times with a car wash machine under the condition of 20 ° C. ° Gloss value) was measured, and the gloss retention rate (%) with respect to the 20 ° gloss value before the test was calculated and evaluated according to the following criteria. The higher the gloss retention rate, the better the scratch resistance. In the present specification, if the evaluation result is A, B or C, it means excellent scratch resistance. As the car wash machine, "PO20 FWRC" manufactured by Yasui Sangyo Co., Ltd. was used.

A: Gloss retention rate of 80% or more B: Gloss retention rate of 75% or more and less than 80% C: Gloss retention rate of 70% or more and less than 75% D: Gloss retention rate of 50% or more and less than 70% E: Gloss retention rate of less than 50%.

Although the embodiments and examples of the present invention have been specifically described above, the present invention is not limited to the above-described embodiments, and various modifications based on the technical idea of the present invention are possible.

For example, the configurations, methods, processes, shapes, materials, numerical values, etc. given in the above-described embodiments and examples are merely examples, and if necessary, different configurations, methods, processes, shapes, materials, numerical values, etc. May be used.

Further, the configurations, methods, processes, shapes, materials, numerical values, etc. of the above-described embodiments can be combined with each other as long as they do not deviate from the gist of the present invention.

The present invention can also adopt the following configurations.
[1] A coating composition containing (A) a binder component, (B) a first viscosity modifier, and (C) a second viscosity modifier.
The first viscosity modifier (B) is
It is a non-water dispersion resin (b) and
The second viscosity modifier (C)
(C1) Polyisocyanate compound,
(C2) Contains a reaction product of a primary monoamine having a number average molecular weight of 300 or less and a polyether amine having two or more (c3) amino groups and having a number average molecular weight of 1000 or more and less than 6000.
The blending ratio of the polyether amine (c3) having two or more amino groups and having a number average molecular weight of 1000 or more and less than 6000 is 10 based on the total amount of the components (c1) to (c3). A coating composition in the range of ~ 30% by mass.
[2] The coating composition according to [1], wherein the polyether amine (c3) having two or more amino groups and having a number average molecular weight of 1000 or more and less than 6000 has three or more amino groups.
[3] The blending ratio of the polyether amine (c3) having two or more amino groups and having a number average molecular weight of 1000 or more and less than 6000 is based on the total amount of the components (c1) to (c3). The coating composition according to [1] or [2], which is 15 to 30% by mass.
[4] Any of [1] to [3], wherein the compounding ratio of the polyisocyanate compound (c1) is 30% by mass to 60% by mass based on the total amount of the components (c1) to (c3). The coating composition according to item 1.

[5] The blending ratio of the primary monoamine (c2) having a number average molecular weight of 300 or less is 30% by mass to 60% by mass based on the total amount of the components (c1) to (c3) [1]. ] To the coating composition according to any one of [4].
[6] The non-aqueous dispersion resin (b) includes a polymer dispersion stabilizer (b1) and acrylic resin particles (b3) obtained by polymerizing at least one polymerizable unsaturated monomer (b2). The coating composition according to any one of [1] to [5].
[7] The coating composition according to any one of [1] to [6], wherein the binder component (A) contains a hydroxyl group-containing resin (A1) and a cross-linking agent (A2).
[8] The coating composition according to [7], wherein the hydroxyl group-containing resin (A1) is a hydroxyl group-containing acrylic resin (A1-1).
[9] The coating composition according to [7] or [8], wherein the hydroxyl group-containing resin (A1) contains a secondary hydroxyl group-containing acrylic resin (A1-1a).
[10] The coating composition according to any one of [7] to [9], wherein the hydroxyl group-containing resin (A1) contains an acrylic resin (A1-1b) having a hydroxyl group and an alkoxysilyl group.
[11] The coating composition according to any one of [7] to [10], wherein the hydroxyl group-containing resin (A1) contains an acrylic resin (A1-1c) having a secondary hydroxyl group and an alkoxysilyl group.
[12] The cross-linking agent (A2) contains one or more polyisocyanate compounds, and the content ratio of the polyisocyanate compound is 5 to 60 parts by mass based on 100 parts by mass of the total solid content of the binder components. The coating composition according to any one of [7] to [11].
[13] The cross-linking agent (A2) contains a blocked polyisocyanate compound, and the content ratio of the blocked polyisocyanate compound is 5 to 60 parts by mass based on 100 parts by mass of the total solid content of the binder components [7]. The coating composition according to any one of [11].

[14] The cross-linking agent (A2) contains an amino resin, and the content ratio of the amino resin is 0.5 to 40 parts by mass based on 100 parts by mass of the total solid content of the binder components [7] to [11]. The coating composition according to any one of the above items.
[15] The content of the first viscosity modifier (B) is 0.5 to 100 parts by mass based on 100 parts by mass of the total solid content of the binder component (A) and the first viscosity modifier (B). It is within the range of 10 parts by mass and
The content of the second viscosity modifier (C) is 0.05 to 1 part by mass based on 100 parts by mass of the total solid content of the binder component (A) and the first viscosity modifier (B). The coating composition according to any one of [1] to [14], which is within the range of.

Claims (4)

A coating composition containing (A) a binder component, (B) a first viscosity modifier, and (C) a second viscosity modifier.
The first viscosity modifier (B) is
It is a non-water dispersion resin (b) and
The second viscosity modifier (C)
(C1) Polyisocyanate compound,
It contains (c2) a primary monoamine having a number average molecular weight of 300 or less, and (c3) a reaction product of a polyether amine having two or more amino groups and having a number average molecular weight of 1000 or more and less than 6000.
The blending ratio of the polyether amine (c3) having two or more amino groups and having a number average molecular weight of 1000 or more and less than 6000 is 10 based on the total amount of the components (c1) to (c3). A coating composition in the range of ~ 30% by mass. The coating composition according to claim 1, wherein the polyether amine (c3) having two or more amino groups and having a number average molecular weight of 1000 or more and less than 6000 has three or more amino groups. The blending ratio of the polyether amine (c3) having two or more amino groups and having a number average molecular weight of 1000 or more and less than 6000 is 15 based on the total amount of the components (c1) to (c3). The coating composition according to claim 1 or 2, which is in the range of about 30% by mass. The coating composition according to any one of claims 1 to 3, wherein the binder component (A) contains a hydroxyl group-containing resin (A1) and a cross-linking agent (A2).